Embed Size (px)
Citation preview
Surface Chemical Analysisby XPS and SIMS
Prof Ian W Fletcher
Surface Engineering amp Analysis Laboratory
School of Mechanical and Systems EngineeringNewcastle UniversityStephenson BuildingClaremont RoadNewcastle upon TyneNE1 7RU
Tel (office M35) +44 (0)191 208 6788(lab G15a) +44 (0)191 208 5857(mobile) +44 (0)7754 735869
email ianfletchernclacuk
wwwnclacuknexus1
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
Outline
bull SEAL
bull XPS and SIMS
bull What information is available
bull Examples
bull Conclusions
2
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
The Surface Engineering and Analysis Laboratory - SEAL
3
- a means to onersquos ends or an end to onersquos means
SEAL
NEXUSNational EPSRC XPS
Usersrsquo Service
New Ion Beam Tools- ToFSIMS- Helium Ion
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull tendency to avoid surface analysis because it is too expensive
bull commercial charges up to pound3000 per day
bull EPSRC Mid-range XPS facility at Newcastle ndash lsquoNEXUSrsquofree to EPSRC fundable researchers
bull SEAL Ion Beam Toolsmay need to make a small charge to cover running costs
bull SEAL has the best instrument base for surface analysis in Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
4
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull not here
bull means to onersquos ends helliphelliphelliphelliphellip
5
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Outline
bull SEAL
bull XPS and SIMS
bull What information is available
bull Examples
bull Conclusions
2
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
The Surface Engineering and Analysis Laboratory - SEAL
3
- a means to onersquos ends or an end to onersquos means
SEAL
NEXUSNational EPSRC XPS
Usersrsquo Service
New Ion Beam Tools- ToFSIMS- Helium Ion
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull tendency to avoid surface analysis because it is too expensive
bull commercial charges up to pound3000 per day
bull EPSRC Mid-range XPS facility at Newcastle ndash lsquoNEXUSrsquofree to EPSRC fundable researchers
bull SEAL Ion Beam Toolsmay need to make a small charge to cover running costs
bull SEAL has the best instrument base for surface analysis in Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
4
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull not here
bull means to onersquos ends helliphelliphelliphelliphellip
5
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
The Surface Engineering and Analysis Laboratory - SEAL
3
- a means to onersquos ends or an end to onersquos means
SEAL
NEXUSNational EPSRC XPS
Usersrsquo Service
New Ion Beam Tools- ToFSIMS- Helium Ion
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull tendency to avoid surface analysis because it is too expensive
bull commercial charges up to pound3000 per day
bull EPSRC Mid-range XPS facility at Newcastle ndash lsquoNEXUSrsquofree to EPSRC fundable researchers
bull SEAL Ion Beam Toolsmay need to make a small charge to cover running costs
bull SEAL has the best instrument base for surface analysis in Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
4
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull not here
bull means to onersquos ends helliphelliphelliphelliphellip
5
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull tendency to avoid surface analysis because it is too expensive
bull commercial charges up to pound3000 per day
bull EPSRC Mid-range XPS facility at Newcastle ndash lsquoNEXUSrsquofree to EPSRC fundable researchers
bull SEAL Ion Beam Toolsmay need to make a small charge to cover running costs
bull SEAL has the best instrument base for surface analysis in Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
4
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull not here
bull means to onersquos ends helliphelliphelliphelliphellip
5
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
An end to onersquos means
bull not here
bull means to onersquos ends helliphelliphelliphelliphellip
5
- a means to onersquos ends or an end to onersquos means
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
6
What can we dobull determine the elemental chemical and molecular composition of
the outermost surface regions of organic and inorganic materials using spectroscopy imaging and depth profiling
How do we do itbull X-Ray Photoelectron Spectroscopy XPS or ESCA
bull Static Secondary Ion Mass Spectrometry SSIMS
bull Dynamic Secondary Ion Mass Spectrometry DSIMS
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
7
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
8
What is a surface
~1microm
1-10 nm
Sampling Depths
SEM EDXIR Raman
SSIMS ~1nmXPS ~10nm
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
9
Real surfaces arerarely pure materials
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface ne Bulk material
Segregation Surface EngineeringMigration coatingsPhase Separation treatmentCrystallinity flame plasma EBMW chemicalContamination AdsorptionDegradation Corrosion
tribology Oxidationheat light etc Hydrolysischemical
What is on thereSurfactants PolymersAnti-oxidants ResinsLubricants slip agents BiomaterialsMould Release agents OligomersInorganicsContaminantsReaction Process deposits etc
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
10
XPS (ESCA)
X-rayshν
~ 5nm
hν = KE + BE + φe-
KE = hν - BE - φ
BE = hν - KE - φφ
BE
KE
hν
Binding EnergyKinetic Energy
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
11
λ vs photoelectron KE
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
12
Aluminium foil
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Binding Energy eV
Inte
nsity
cp
s
Auger peaks
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
13
Aluminium foil
O 1s C 1s Al 2p
Mg 1s
C kvv
O kllAl 2s Al 2p
C 1s
O 1s
Mg kllMg 2s Mg 2p
VB
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
14
Ultra-highVacuum Chamber
~ 5nm
X-Rays
Sample
emittedphotoelectrons
e-
X-RaySource
Electron EnergyAnalyser
SpectrumImage
I
Energy
O1s
N1s
C1s
XPS (ESCA)X-ray Photoelectron Spectroscopy
bull detects all elements except Hbull detects 1 atom in 1000bull sampling depth from ~ 1nm to ~ 10nmbull relative quantification of elements and chemistrybull chemical information rArr bonding oxidation state
functional groups etc
bull 1-D linescansbull 2-D imaging at ~ 2microm resolutionbull 3-D depth profiles
bull solids and liquidsbull electrical conductors and insulatorsbull analysis at -150degC up to 600degCbull automation
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
15
PET
coating
O1s C1s
N1s
VB
Okll
Relative Atomic Percentage Compositions - number density
271(286)
729(714)
249 73120
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
16
PET
C1s O1s
N1s
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
17
Valence Band
Valence Band
PET
coating
O2s
C2s C2p+O2p
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
18
θ = 90deg
Samplingdepth d 3λ d= 3λsinθ
3λ
θ = 30deg
Tilt the sample to change the photoelectron lsquotake off anglersquoAngle resolved XPS
λ = inelastic mean free path between collisions lsquoimfprsquo
I Itotal = 1 - e -nλ
n of total signal1 6322 8653 9504 9825 9936 997
Typical sampling depths (lsquo3 λrsquo)~10nm in organic materials~5nm in oxides~3nm in metals
d
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
19
Angle-resolved XPS
bull tilt the sample hellip ARXPS
or
bull collect photoelectrons leaving the surface from a range of angles at the same time hellip PARXPS
Thermo lsquoThetaprobersquo
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
20
316L Stainless Steel Surface ndash etched and air exposed
~ 25 depth nm ~10Tardio et al Comparative study of the native oxide on 316L stainless steel
J Vac Sci Technol A 33 (5) 2015
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
21
Imaging XPS
bull element and chemical state imagesbull 2microm spatial resolution
bull Useful to align small area spectroscopy
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
22
Al on Si SEM test pattern
Si image used to define55microm analysis areas
700 x 300microm
Si area
Al area100microm Al bars100microm Si squares 400microm FOV
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
23
Al on Si SEM test pattern - 100microm bars
ldquoHyperspectral Imagingrdquobull Record images at different BErsquosbull Select area rArr regenerate spectra
O1s images 533 - 527eV 02eV step
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample damagelsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
24
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
What is SIMS
25
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
0 20 40 60 80 100 120 140 160 180 200
200 220 240 260 280 300 320 340 360 380 400
400 420 440 460 480 500 520 540 560 580 600
mz
Mass Spectrometer
lt1nm
Primary ionsSecondary ions
20microm
SSIMSStatic Secondary Ion Mass Spectrometry
26
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
sputtered moleculesfragmentsionsatomselectronsphotons
mixing implantation sampling
10nm 8nm 1-2nm
primary ion
SSIMS
27
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
SSIMSStatic Secondary Ion Mass Spectrometry
28
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Any type of mass spectrometer can be used
Quadrupole
Magnetic sector
Time-of-Flight rArr lsquoToFSIMSrsquo
bull high transmission = high signal levels
bull parallel detection = fast acquisition
bull high mass resolution
bull pulsed system
SSIMSStatic Secondary Ion Mass Spectrometry
29
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
wwwiontofcom
TOFSIMS
30
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
The Ion-Tof lsquoToF-SIMS IV ndash 200rsquo Instrument
bull 8rdquo sample capabilitybull automationbull -150degC to 600degC
bull Ga+ In+ Aun+ Bin+ SF5
+
Cs+ Ar+ and O2+ ion
sources
high signal levels for molecular species
imaging of molecularspecies at ~ 03microm resolution
31
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
The Ionoptika J105 SIMS
Not only C60+ and Ar4000
+ but also
[H2O]6000+ cluster ion beam source helliphellip
32
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Ionoptika J105 SIMS
33
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull Detects all elementsbull Mass range up to 20000 Dabull ppm - ppb sensitivity
bull Spectrometry ndash lsquofingerprintrsquo characteristic spectra from Static SIMSndash molecular identification of organic and inorganic speciesndash relative quantification of molecular speciesndash high mass resolution (m∆m ~10000+)
bull Imagingndash 03microm resolution
bull Depth profiles ndash inorganic and organic materialsndash ~1nm depth resolution
What information is available
34
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull lsquoRetrospectiversquo spectrometry imaging and depth profilingndash Every 2D pixel or 3D voxel contains a full mass spectrum
bull Solids and liquids
bull Electrical conductors and insulators
bull Analysis at -150degC up to 600degC
ndash Thermal Desorption SIMS
What information is available
35
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
High Mass-Resolution SSIMS
bull m∆m = 10000+bull identify ion composition from accurate massbull resolve inorganic from organic species (eg Fe+ C4H8
+)bull elemental and molecular informationbull ppm sensitivitybull novel informationbull facilitates relative quantification
bull probe active surface chemistrybull identify poisons deactivation mechanismsbull oxidation state informationbull compound identification
36
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
37
30Si+29SiH+
28SiH2+
C2H6+
CH2NH2+
CH2O+
NO+
Si wafer mz 30
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
7095 71 7105 711 71150
1000
2000
3000
mz
Cou
nts
Untreated
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 1
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 2
7095 71 7105 711 71150
2000
4000
6000
mz
Cou
nts
Treatment 3
C4H7O C5H11C3H3O2
U
T1
T2
T3
Positive ionhigh mass resolutionSSIMS spectra
mz +71
Discrete peak areas
Relative quantification
38
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull Topography independent mass resolution
also Large Depth of Field
Cr image of an M16 screw
39
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
410390 43040
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 600041K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
410405 41
MR = 41
41
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
C3H5+
mz +41
MR = 1000
MR = 6000
41K+
29SiC+
28SiCH+
40CaH+
C13CO+
40Ca42Ca2+
500microm x 500microm
750microm x 750micromJ105
lsquoTraditionalrsquo design (Iontof PHI)
42
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Imaging SSIMS
Molecular species elements small fragment ionsca 300nm spatial resolutionlsquoHyperspectralrsquo Imaging - every pixel contains a full mass spectrum
Sciencedistribution location of speciesstructure property relationshipsmigration studiescoating defects small area analysis
Sales and Marketinggetting the message acrossldquoIf I canrsquot picture it I canrsquot understand itrdquo
43
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Total Ion Image PET trimermz +577
Segregation of PET trimer
Heated PET film
30microm
44
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
20microm
Single 50microm particle on a 35rdquo Floppy Disk surface
Imaging SSIMS analysis
bull each pixel has a full mass spectrumbull select defined small areasbull regenerate spectra
PET particle on top of coating
bull clean upbull modify machinery
bull 100 pass rate for particulatesbull reduced costs
45
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Coating problem
unexpected segregation of 2 coating componentsidentified by SSIMS
product not working at all6 months wasted project time
process modifiedrepeatable uniform coverage
product working as predicted
250microm x 250microm
46
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of coated polymer microspheres
30microm
Surfactant Contaminant
XPS indicated the average surfactant thickness = 09nm
Surfactant (green)Contaminant (red)
47
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
500microm x 500microm
Total Ion Image Diglycerides Na (green)Flavour Enhancer (red)
Static ToFSIMS images of a flavoured potato crisp
48
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
10microm 10microm
50microm 10microm
Molecular SSIMS images from human hair showing various treatment residues49
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene fibres used in nappiesProduct Performance depends on
bull Fibre surface chemistry treatmentbull Surface coveragebull Porosity of the non-woven fabric
bull lsquoESCrsquo treatment more uniformly distributedbull lsquoESCrsquo treated fabric outperforms competitive materials
ESC Competitor20microm
50
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
SSIMS Images of Polypropylene carpet fibres
ldquoA picture paints a thousand wordshelliprdquoESC
30micromCompetitor
bull Tri-lobal fibresbull Treatment to reduce friction during processingbull lsquoESCrsquo treatment applied at 5x lower levelbull Outperformed competitive treatmentsbull Images used for Sales amp Marketing
51
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Detection of Volatile Materials
250microm x 250microm 128microm x 128microm
Fragrances on Human hair
bull small molecules volatile mobile species analysis at -110 degC
bull treatment shown in lsquoyellow redrsquo [M-H]-
52
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Secondary Ion Mass Spectrometry ndash lsquoSIMSrsquo
lsquoStaticrsquo mode lsquoDynamicrsquo modeSSIMS DSIMS
Low sample damage High sample lsquodamagersquolsquoFingerprintrsquo spectra Composition depth profiles
Primary Ion Dose Densitylt1x1012 ions cm-2 gt1x1013 ions cm-2
Typical surface = 1x1015 atoms cm-2
53
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
0 5 10 15 20 25 30 35 40 45100
101
102
103
104
105
30Si+
11B+
Inte
nsity
co
unts
depth nm
1017
1018
1019
1020
1021
1022
11B
con
cent
ratio
n a
tom
scm
3
00 05 10 15 20 25 30
4x1020
6x1020
8x1020
1x1021
11B
con
cent
ratio
n a
tom
scm
2
depth nm
wwwiontofcom
Sample700 eV B+ implant in Silicon
54
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Depth Profile 2D Cross Section 3D Render
Overlay Imagered Al2green Inblue Ga2
red Al2green Ingrey GaAlblue Ga2
Field of View 60 x 60 microm2
3D Distributionexample Al2+GaAl
wwwiontofcom55
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Depth Profiling ndash Dynamic SIMS
56
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Typical Questions Asked
Specific
bull Is there any X presentbull How much is presentbull How is it distributed
bull 1- or 2-Dbull depthbull 3-D
bull Locus of failure
General
bull What is itbull Where is itbull What is different between good
and bad samplesbull Why is it failingbull Why wonrsquot it stick
bull adhesionbull laminatesbull printing coating
bull Why is theirs better than ours
RampT Production Process monitoring development QC Patent protection SHE
57
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
58
Typical applications
bull failure analysis ndash laminates metallised layers heat-sealadhesive joints coating issues
bull coating defectsbull printing defectsbull adhesive developmentsbull materials developments bull surface pre-treatmentbull primer developmentsbull contaminationbull corrosion studiesbull additive migration bloombull competitive material analysisbull pharmaceutical medicalbull hellip
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Latest developments hellip
bull Topography independent mass resolution
bull C60+ ion source
bull Ar4000+ cluster ion source
bull (H2O)6000+ cluster ion source
bull Mass Spec ndash Mass Spec MSMS
bull 10nm spatial resolution
bull SALVI
59
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull C60+ ion source
ndash 200nm spatial resolution
ndash enhanced signal levels for molecular species
ndash organic inorganic and mixed depth profiling
ndash analysis of buried interfaces
60
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
NIST NiCr sample 66 and 53 nm alternating layers C60+ ion source
Depth Profiling ndash Dynamic SIMS
61
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull Ar4000+ cluster ion source
ndash 500 1000 2000 and 4000 cluster sizes
ndash 2 micron spatial resolution
ndash analysis of real (contaminated) samples
ndash enhanced signal levels for molecular species
ndash organic depth profiling
ndash analysis of buried interfaces
62
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Imaging intact lipid species in mouse brain tissue
Large Image is 25 times 25 mm210 micrompixel
Detailed image has area 512 x 512 mm2 acquired at 2 micrompixel
Dose of 6e12 negative ion mode
63
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Single peak mass images full mass spectrum available at each pixel
mz 8874 PI(383)mz 7884 PS(361)mz 6874 SM(331)
Freeze dried biopsy tissue
0E+00
1E+05
2E+05
3E+05
500 600 700 800 900
coun
tsmz
Stroma
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Cancerous Region
0E+001E+052E+053E+05
500 600 700 800 900
coun
ts
mz
Dead Tissue
64
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Tissue Imaging with Ar4000 on frozen hydrated tissue section
All data was acquired using 40 keV Ar4000
+ ion dose 1 times 1012
ionscm2 negative ion mode FOV is 5 mm
65
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Depth profiling of Organic Materials
SSIMS destroys the surface
bull How to get more useful signal from the same amount of surface
bull Use cluster ion beams eg Auxn+ Bixn+ Ar4000
+
or polyatomic ions SF5+ C60
+ C24H12+
or low energy Cs+ eg 200eV
bull Lower impact energy per atomndash less mixing fragmentation and sub-surface damage
bull More signal from molecular species for a given ion doseeg Bi32+ ca 50000 x Ga+
bull No apparent damage66
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
t=29 ps
15 keV Ga+ 15 keV C60+
C60 bombardment calculations Zbigniew Postawa Enhancement of Sputtering Yields due to C60 vs Ga Bombardment of Ag111 as Explored by Molecular Dynamics Simulations Z Postawa B Czerwinski M Szewczyk E J Smiley N Winograd and B J Garrison Anal Chem 75 4402-4407 (2003) Microscopic insights into the sputtering of Ag111 induced by C60 and Ga Bombardment ibid J Phys Chem B 108 7831-7838 (2004)
bull Larger volume is altered for Gabull 15x more material removed with C60
67
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
68
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
69
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Depth profiling of organic materials using polyatomic ions Bixn+ SF5+ C60
+
Ar2500+
Thick polymer coating containing drug on substrate
drug
polymer
substrate
Thin polymer layer on Si substrate
~ constant signal from molecular species
70
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Modern Gas Cluster Ion Sources allow depth profiling through organic materials and devices with little or no damage to the molecular
structures hellip
71
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
3D Imaging Static SIMS - Yucca plant leaf
72
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull Full mass spectrum in each 2D pixel or 3D voxel
bull Big datafiles 1TB+
bull Principal Component Analysis bull Usually a slow process
bull New algorithm - PJCbull Very fastbull 10 seconds vs 27 hours
bull Quickly screen databull Reprocess to ID chemistry etcbull Overall a very powerful toolkit
3D Imaging Static SIMS - Yucca plant leaf
73
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull (H2O)6000+ cluster ion source
ndash 10 to gt100x more signal for protonated species compared to Ar4000
+
ndash 2 micron spatial resolution
ndash lower detection limits
bull analysis of real therapeutic dose levels
bull trace analysis
74
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull Mass Spec ndash Mass Spec MSMS
ndash Collision Induced Dissociation of secondary ion species produces spectra that are similar to lsquonormalrsquo mass spectra
ndash comparison with standard databases
ndash facilitates identification interpretation
75
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
MSMS of mz 49545
x50
DAG region of fly brain spectrum
MSMS of Diacylglycerides in Fly brainHigh energy CID (05 ndash 6 keV)Nitrogen collision gasToF-ToF
Povides detail on chain lengths and saturation and there increased specificity that tells us about the biology
76
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
bull 10nm spatial resolution
ndash Magnetic Sector upgrade to Zeiss Orion HIM
ndash Ne+ primary ions
77
Latest developments hellip
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
78
Examples of Applications
bull Based on real examples and real data
bull Some details changed to preserve confidentiality etc
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
79
Na 1sK 2s
N 1s
S 2p
Cl 2p
Aluminium foil
Aluminium foil + fingerprint
Mg 1s
C kvvO kll
Al 2s Al 2pC 1s
O 1s
Mg kllMg 2s Mg 2p
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
80
Relative Atomic Percentage Composition
Al foil ContaminatedMg 5 02O 58 24C 10 65Al 27 8
Na - 08K - 11Cl - 06S - 04
Canrsquot touch the sample for analysis
Care also with sample packaging
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
81
Ag foil used for adhesive developments
Rel At CompAg C O
As received 51 40 9
Solvent wipe 02 85 15
Solvent wipe + rinse 03 85 15
Ultrasonic washing 35 43 22
Polymer surfaces more favourable than metals but bewareSolvent purity contaminationPlastic wash-bottlesContaminated glasswareExtractables in tissues cloths etc
Surface contamination and cleaning
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
82
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
bull very common family of materialsbull many applications (lubricant release agent anti-foamerhelliphelliphellip)bull mobile spreads easilybull cannot easily distinguish siloxanes from silicates by XPSbull very characteristic SSIMS spectra
bull enough silicone manufactured to cover the surface of the Earth to a level of several nm deep
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
83
Poly(dimethylsiloxane) PDMS
CH3|
( - Si - O - )n|CH3
Typical example
bull Polymer material used in adhesive applicationbull One lsquoGoodrsquo sample one lsquoBadrsquobull Whybull XPS 10 Si on Good 20 on Bad (Pure PDMS = 25 Si)bull SSIMS dominated by PDMS signal
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Cou
nts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Cou
nts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Cou
nts
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
84
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
85
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additiveICI
Acq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
86
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
87
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
88
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
89
lsquoOily ragrsquo syndrome
bull Streaks and smears on extruded product hellipbull Extruder lips cleaned with a proprietary domestic spray cleanerbull lsquoSilicone freersquo according to manufacturer
bull Anti-foam additive
bull Always shoot the man with theoily rag
bull Cleanroom example hellipbull Aerospace example hellipbull Automotive example hellip
ICIAcq 98 May 13 +ToFSIMS 80 keV Cs+ Cal yes AcqTime 272 min Bin 6621 nsPulses 819200 Integral 1204014 Max 49394 Approx MnMw 24162451
100 110 120 130 140 150 160 170 180 190 2000
05
1
15
2x 10 4
mz
Coun
ts
0 10 20 30 40 50 60 70 80 90 1000
05
1
15
2x 10 5
mz
Coun
ts
200 210 220 230 240 250 260 270 280 290 3000
2000
4000
6000
mz
Coun
ts
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
90
High speed failures of novel suspension component
bull 3 major testing accidents at 170mph+bull adhesive failure between CF and Ti componentsbull cause traced to inadequate cleaning of machined Tibull fixed in time for the final races of 2001 seasonbull won the race amp Drivers and Constructors championships
bull new suspension design also used in 2002 2003 2004helliphellip
Ti
Adhesive film
Carbon Fibre component
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
91
Not only fingerprints and PDMS but also
bull hydrocarbonsbull fluorocarbonsbull amidesbull anti-oxidantsbull UV stabilisersbull mould release agentsbull surfactantsbull mobile additivesbull oligomersbull particulatesbull hellip
bull one manrsquos product is another manrsquos contaminant
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
92
Failed coating example
bull high-end vehicle doors ndash extra holes in the door panel cut by hand to fit new lock design
bull painted as normal
bull paint blisters forming after several months service hellip
bull ToFSIMS analysis from underside of paint flake
traces of original cutting fluid
inadequate cleaning after cutting
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
93
Failed coating example
bull internal coating on pipework failing leading to corrosion
bull offshore application ndash expensive and difficult to repair
bull repeating pattern noticed every few metres along the pipe helliphellip
bull ToFSIMS analysis
traces of high pressure hydraulic oil between the coatingand the steel pipe surface
pipe manufacturing process issue identified
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
Pretreat 1
PET
Pretreat 2
Metal
Pretreat 1 optimised for print adhesion
Pretreat 2 optimised for metal adhesion
Failure between metal and pretreat ldquo2rdquo
Why
94
Failed coating example
bull Bottle label falling off during re-use washing cycle
bull expected sequence wash rinse remove label
Glass
adhesive
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
95
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
XPS SIMS analysis of a coated can
metal processing cleaning inner coating outer coating printing lacquer
96
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
97
Plane of failure analyses
bull Packaging laminate
Sample after delamination
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PETAdhesion Pretreat
AdhesivePE
PETAdhesion Pretreat
PrintAdhesive
Aluminium MetalAdhesive
PET
Adhesion PretreatAdhesive
PE
Metal side
Film side
Failure surfaces
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
98
Identification of an Unknown Green Slime by XPS
Sample Relative Atomic Percentage Composition
C S O Cr Unknown 644 82 247 27 Cr Tosylate 618 88 265 29
(CH3-C6H4-SO3-)3Cr
Significant aromatic character in C1s spectrumOS ratio ~ 31SCr ratio ~ 31Cr as Cr III S oxidised sulphate or sulphonate-like
Overall results consistent with
bull Urgent problem - what is it and where did it come frombull Sample dried in air at 50degC for 1 hour
Surface Chemical Analysisby XPS and SIMS
99
Cr VI
Cr(OH)3
Cr2O3
Cr metal
XPS data
11 Cr40 as Cr VI
6 Cr10 as Cr VI
Determination of Cr VI content by XPSCr 2p high resolution spectra
Sampling depth3-5nm
Surface Chemical Analysisby XPS and SIMS
100
Overlayer - substrate interactions
bull Compare thin layer with a relatively thick layerbull Overlayer thickness determination
samplingdepth
molecules interacting with the surface
substrate
Surface Chemical Analysisby XPS and SIMS
101
samplingdepth
bull Compare thin layer with a relatively thick layerbull Overlayer thickness determination
Overlayer - substrate interactions
molecules interacting with the surface
molecules interacting with molecules
substrate
Surface Chemical Analysisby XPS and SIMS
102
Bond Type EnergykJmol-1
Ionic 600-1100Covalent 60-700Metallic 110-350
Broumlnsted Acid-Base Up to 1000Lewis Acid-Base Up to 80
Hydrogen Bonds (incl F) Up to 40Hydrogen Bonds (excl F) 10-25Permanent Dipole-Dipole 4-20
Dipole-Induced Dipole lt 2Dispersion Forces 008-40
prim
ary
bond
sse
cond
ary
bond
s
van
der
Waa
ls b
onds
Surface Chemical Analysisby XPS and SIMS
103
Adsorption Isotherms
bull XPS provides reliable quantitative surface chemical analysis
bull ToF-SIMS provides semi-quantitative molecular data
bull Both can be used to estimate density of bonding sites and bond type
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
100
Overlayer - substrate interactions
bull Compare thin layer with a relatively thick layerbull Overlayer thickness determination
samplingdepth
molecules interacting with the surface
substrate
Surface Chemical Analysisby XPS and SIMS
101
samplingdepth
bull Compare thin layer with a relatively thick layerbull Overlayer thickness determination
Overlayer - substrate interactions
molecules interacting with the surface
molecules interacting with molecules
substrate
Surface Chemical Analysisby XPS and SIMS
102
Bond Type EnergykJmol-1
Ionic 600-1100Covalent 60-700Metallic 110-350
Broumlnsted Acid-Base Up to 1000Lewis Acid-Base Up to 80
Hydrogen Bonds (incl F) Up to 40Hydrogen Bonds (excl F) 10-25Permanent Dipole-Dipole 4-20
Dipole-Induced Dipole lt 2Dispersion Forces 008-40
prim
ary
bond
sse
cond
ary
bond
s
van
der
Waa
ls b
onds
Surface Chemical Analysisby XPS and SIMS
103
Adsorption Isotherms
bull XPS provides reliable quantitative surface chemical analysis
bull ToF-SIMS provides semi-quantitative molecular data
bull Both can be used to estimate density of bonding sites and bond type
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
101
samplingdepth
bull Compare thin layer with a relatively thick layerbull Overlayer thickness determination
Overlayer - substrate interactions
molecules interacting with the surface
molecules interacting with molecules
substrate
Surface Chemical Analysisby XPS and SIMS
102
Bond Type EnergykJmol-1
Ionic 600-1100Covalent 60-700Metallic 110-350
Broumlnsted Acid-Base Up to 1000Lewis Acid-Base Up to 80
Hydrogen Bonds (incl F) Up to 40Hydrogen Bonds (excl F) 10-25Permanent Dipole-Dipole 4-20
Dipole-Induced Dipole lt 2Dispersion Forces 008-40
prim
ary
bond
sse
cond
ary
bond
s
van
der
Waa
ls b
onds
Surface Chemical Analysisby XPS and SIMS
103
Adsorption Isotherms
bull XPS provides reliable quantitative surface chemical analysis
bull ToF-SIMS provides semi-quantitative molecular data
bull Both can be used to estimate density of bonding sites and bond type
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
102
Bond Type EnergykJmol-1
Ionic 600-1100Covalent 60-700Metallic 110-350
Broumlnsted Acid-Base Up to 1000Lewis Acid-Base Up to 80
Hydrogen Bonds (incl F) Up to 40Hydrogen Bonds (excl F) 10-25Permanent Dipole-Dipole 4-20
Dipole-Induced Dipole lt 2Dispersion Forces 008-40
prim
ary
bond
sse
cond
ary
bond
s
van
der
Waa
ls b
onds
Surface Chemical Analysisby XPS and SIMS
103
Adsorption Isotherms
bull XPS provides reliable quantitative surface chemical analysis
bull ToF-SIMS provides semi-quantitative molecular data
bull Both can be used to estimate density of bonding sites and bond type
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
103
Adsorption Isotherms
bull XPS provides reliable quantitative surface chemical analysis
bull ToF-SIMS provides semi-quantitative molecular data
bull Both can be used to estimate density of bonding sites and bond type
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
104
500microm x 500micromTreated Metal Surfacebull 2 additives A and Bbull competitive adsorption onto metal surfacebull ~4 nm thick layerbull TD SSIMS analysis from 30 - 400 degCbull use of molecular ions for each additivebull estimate desorption energies from T at the
maximum rate of desorption
XY at surface
XZ or YZ
ldquoThermal Desorptionrdquo SSIMS
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
105
45 degC
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
106
60 degC
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
107
75 degC
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
108
90 degC
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
109
105 degC
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
110
120 degC
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
111
135 degC
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
112
150 degC
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
113
165 degC
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
114
195 degC
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
115
225 degC
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
116
255 degC
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
117
285 degC
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
118
315 degC
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
119
θ ~ 002deg
d ~ 03 microns per mm03nm per micron
θ
Buried Interfaces amp Depth Profiling of Organic Materials
bull Ultra Low Angle Microtomy - ULAMbull small samplesbull glass diamond knifebull prepare many samples
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
120
Depth Profiling of Organic Materials
bull ULAM
image
linescan
lsquobulkrsquo vs interface
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
121
Depth Profiling of Organic Materials
bull ULAM
bull sampling depths
XPS ~ 10nm SSIMS ~ 1nm
bull spatial resolution depth resolution
XPS ~ 55 x 55 microm = ~ 17 nm at 002deg SSIMS ~ 100 x 100 microm = ~ 30 nm iSSIMS ~ 1microm = ~ 1 nm
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
122
Depth Profiling of Organic Materials
bull ULAMbull spreading of mobile speciesbull cut inside to out as wellbull cryo prep
θ ~ 002degd ~ 03 microns per mm
03nm per micron
θ
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
123
Depth Profiling of Organic Materials
bull ULAMPanel 16 Linescan
0
10
20
30
40
50
60
70
80
90
-550 -450 -350 -250 -150 -50 50 150 250
Depth microm
Rel
ativ
e A
tom
ic P
erce
ntag
e C
ompo
sitio
n
0
2
4
6
8
10
12
O 1sC 1sF 1sTi 2pN 1sSi 2pMg 2sAl 2p
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
124
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
125
Depth Profiling of Organic Materials
bull ULAM
0
1000
2000
3000
4000
5000
6000
7000
8000
00 20 40 60 80
Depth Microns
Inte
nsity
C
ount
s
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
126
Depth Profiling of Organic Materials
bull ULAM
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
127
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
No emissions
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
128
Catalyst deactivation problem
bull Problem encountered during commissioning of a new plant design
bull Exhaust catalyst damaged withinminutes of start-up
Why
Fit a new pound05M catalyst or not
Urgent problem received on a Friday evening
Initial SSIMS and XPS analysis hellip
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
Note Br present at ~ 5 atoms in 1000 by XPS
Bromomethane present in exhaust gas stream at low level
BUT ndash no reaction with catalyst under any conditions
200 250 300 350 400 450 5000
200
400
600
800
1000
mz
Counts
200 250 300 350 400 450 5000
500
1000
1500
mz
Counts
PtPtO
PtO2
Pt2O2
-
-Pt
PtBr
PtBr2
PtBr4
PtBr3
Active Catalyst
Deactivated Catalyst
129
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
52 54 56 58 60 62 640
500
1000
1500
mz
Cou
nts
C4H7
C4H9
C3H8N
C4H5
C4H6
C4H8
Fe- C5H5
C5H3
52 54 56 58 60 62 640
100
200
300
400
500
mz
Cou
nts
Cu
Cu
ActiveCatalyst
DeactivatedCatalyst
+
+
Note Cu present at only 1 atom in 1000 by XPS
130
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
131
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
132
Catalyst deactivation problem
HeatExchangers
Exhaust Gas
Scrubbers
Catalyst BedGas torches
bull root cause identifiedbull temporary fixbull longer term solution pound10M cost
bull saved pound05M catalystbull license to operate pound200M investmentbull reputation
bull 2 similar plant designs hellip
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
133
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull XPS and SIMS should be considered whenever surface
chemistry is involved or when surface chemical information is required
bull Very powerful capabilities at SEAL ndash available to all
bull Capability = f equipment people (experience + ability)
bull Enabling support for research and development
bull Problem solving support for processes and production
bull Pushing the limits
bull If you have a problem if no one else can help and if you can find them maybe you can hire the SEAL Team 134
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull If we canrsquot do it it probably canrsquot be done
135
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
Surface Chemical Analysisby XPS and SIMS
Conclusionsbull SEAL has the best instrument base for surface analysis in
Europe including XPS ToFSIMS Gas Cluster Ion Beams and Helium Ion Microscopy facilities
bull Also UPS ISS SEM EDX FIB AES AFM SPM QCM GDOES White-Light Interferometry and Raman Microscopy
bull Thank you for the invitation and for your attention
136
