LEARNING CHECK - Instrumental Analysis · Transmission Electron Microscopy (TEM ... hfp:// SEM POLLENS 2/22/16 10 SEM IMAGES ... - X-ray techniques

2/22/16

1

LOOKINGAHEADMonday(Feb22)-Electronmicroscopy

Tuesday/Thursday(Feb23,25)-Experiment3-ColorsandCalories

DueTuesday:Experiment2Report

DueThursday:Experiment5Procedure?

Monday(Feb29)-X-raytechniquesDue:Experiment1Report?

LEARNINGCHECK

2/22/16

2

ERRORFAMILYTREE

Error

RandomGross SystemaAc

Instrumental MethodPersonal

Flicker(1/f) ChemicalEnvironmentalThermalor

Johnson Shot

WHATKINDOFINSTRUMENTISPICTURED?HOWDOYOUKNOW?

InstrumentA

Det

ecto

r

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InstrumentBSource

Sample

Wavelength selector

Detector


InstrumentC

Detector

Source

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InstrumentD

Sample

Detector


InstrumentE

Detector 2

Detector 1

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InstrumentF

Source

Sample

WHATKINDINSTRUMENTISPICTURED?HOWDOYOUKNOW?

InstrumentG

Source

Detector

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WHATKINDOFINSTRUMENTISPICTURED?HOWDOYOUKNOW? InstrumentH


InstrumentISource 1

Source 2

Detector

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InstrumentJ

Optical notch filter


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ELECTRONMICROSCOPYCHEM314

OBJECTIVES•  IdenKfydifferentkindsofelectronmicroscopyanddifferenKatebetweenthe

opKmalusesofeach.

•  DescribebasicpartsofEMinstrument:electrongeneraKon,beamcondiKoning,detectors,vacuum

•  ListanddescribepotenKalbeam-sampleinteracKons.DescribehoweachisdetectedandwhattypeofinformaKonisobtained.

HISTORY

1931-ErnstRuskaandMaxKnollconstructedprototypewith400x

1933-EMsurpassedvisiblelightmagnificaKon&resoluKon

1939-firstcommercialTEMproducedbySiemens

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FLAVORSOFELECTRONMICROSCOPYScanningElectronMicroscopy(SEM)

FEIQuanta200OpAmizedforexaminaAonofsampletopographyandmorphology

TEM

EMPA

SEM ElectronMicroprobeAnalysis(EMPA)JEOLJXA-8530FRequiredflatsample(thinsecAon)QuanAficaAonofelements(andminerals)

TransmissionElectronMicroscopy(TEM)

JEOL1200Shapes,density,sizeDiffracAonpafernsandelementalanalysis

hfp://www.telegraph.co.uk/news/science/picture-galleries/

SEMPOLLENS

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SEMIMAGESOFINSECTS

hfp://www.telegraph.co.uk/news/science/picture-galleries/

hfp://www.telegraph.co.uk/news/science/picture-galleries/hfps://dpqe0zkrjo0ak.cloudfront.net/pfil/2650/comet_moth.jpg

MOONORCOMETMOTHFROMMADAGASCAR

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hfp://d32ogoqmya1dw8.cloudfront.net/images/research_educaAon/geochemsheets/techniques/asbestos_3.jpghfp://www.ecfia.eu/img/asbestos-fibres.jpg

SEMNATURALASBESTOS

NICKELALLOYSURFACEWITHDENDRITICSILICA

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COALFLYASH

24BuffaloGrass(Buchloedactyloides)rootApgrowninKlondyketailings(T5.4)with15%w/wcompostaddiAon.GreenhousestudyandFISHperformedbyS.Iverson

25.0kVx14,000SE

4.0um

SoilparAcle

CompostparAcle

RootAp

Bacteria

S3400 25.0KV x500SE

Adhesionoflead-richparAcleXRF

13.00 13.05 13.10 13.150.0

0.2

0.4

0.6

0.8

1.0

1.2

Norm.A

bs.

E nerg y(keV )

chi2=0.34 sum=1.00 PbJar= 0.74 PbSO4= 0.26

25.0kVx14,000SE

4.0um

SoilparAcle

CompostparAcle

RootAp

Bacteria

FISHBacterialimaging

Adhesionoflead-richparAcleXRF

FISHBacterialimaging

XASLeadspeciaAon

Root- Microbe- Mineral- Metal interactions

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TEM

EMPA




PosiKon# Ticontent(ppm)1 33 3 41 4 34 6 36 8 33 10 50 16 51 18 63 20 163 21 146

hfp://www.microscopy-analysis.com/editorials/editorial-lisAngs/do-you-see-ppm-level-differences-mineral-chemistry

TITANIUMINQUARTZBYEMPA

CLdetector

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ELECTRONMICROPROBE:QUANTITATIVEELEMENTALANALYSISRESULTS(WT%)Sample: 362 Flat 368 Big

Grain: 1 2 3 4 5 6 1 2 3 4 5 6

O: 24.1 32.2 24.6 20.8 28.8 34.3 27.6 26.3 28.4 26 21 26.6

F: 0 0.8 0 0 0 0 0 0 0 0 0 0

Na: 0.8 0.9 0 0 0.5 0.1 0.5 0.6 0.5 1.3 0.6 1.8

Mg: 0 0.3 0 0 0.2 0 0 0.2 0.1 0.1 0.1 1.2

Al: 0.3 2.1 0.2 2.4 1.7 0.2 0.3 0.3 0.9 0.2 0.6 1.3

Si: 1.4 5.5 1.1 3.5 1.6 0.4 1.9 1.9 1.5 1.5 4.4 3.5

P: 0.2 0.2 0.2 0.1 0.5 0 0.2 0.1 0.3 0.5 0 0.1

S: 0 0.1 0.2 0.2 0.3 0 0 0.2 0.5 0.3 0 0.4

Cl: 0 0.2 0.1 0.1 0 0 0.2 0.1 0.2 0.3 0 0.2

K: 0 0.8 0 0 0.2 0 0.1 0.3 0.2 0.2 0.1 0.3

Ca: 0.4 0.4 0.4 0.3 0.6 0.1 0.5 0.3 0.5 0.3 7.3 0.3

Ti: 0 0 0 0 0.1 60.4 0.1 0 0 0 0 0

Mn: 0.1 0.1 0.1 0 0 0.1 1.8 0 0.2 0.1 10.7 0.2

Fe: 63.2 48.4 66.7 66.7 60.2 2.3 62.5 67.2 60.5 61.3 2.7 61.7

Cu: 0.5 3.7 0.2 1 0.2 0 0.1 0.3 0.4 1.9 1.1 0.1

Zn: 0 0.7 0 0.2 0.1 0 0.1 0 0.1 0.2 0.2 0.1

As: 0.6 0.4 0.5 0.3 1.5 0 0.1 0.2 0.6 0.9 2.6 0.4

Mo: 0.7 0 0.2 0.3 0 0 0 0.1 0.1 0 1.6 0

Sb: 0.9 0 0.3 0.7 0.8 0.1 0.2 0.2 0.2 0.2 0.3 0

Te: 1.8 2.4 3.5 1.9 2.3 0.6 2.5 0.7 4.5 4.7 30.9 1.7

Tl: 0.4 0.1 0 0.2 0 0.7 0 0.3 0.2 0 0 0

Pb: 0 0.6 0 0 0 0.7 0.3 0.7 0 0 10.6 0

Bi: 4.6 0.1 1.7 1.1 0.1 0 0.9 0 0.2 0 5.2 0.2

Mn

Zn

Mn

Zn

50µm

Hi Low

BSE

50µm

200µm

BSE

Zn association with Mn

200 400 600 800 1000 1200

Birnessite

Johannsenite

Nor

m. i

nten

sity

Raman shift (cm-1)

Manjiroite

MnO2

CaMnSi2O6

KMn8O16·nH2O

birnessite

manjiroitejohannsenite

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Zn association with Mn

2+ 3+ 4+

MnoxidaAonstate

Zn20µm

johannsenite20µm

birnessite20µm

manjiroite20µm

200µm

BSE

6540 6555 6570 6585

Manjiroite

Birnessite

Nor

m. i

nten

sity

Energy (eV)

Johannsenite

MnO2

CaMnSi2O6

KMn8O16·nH2O

10 µm

Quartz

Te-rich material

O

Fe FeFeC

Si

Cu CuMo

Te

TeTe

X-ray Energy (keV) 0 5 10

X-ra

y In

tens

ity 3000

2250

1500

750

0

ELECTRONMICROPROBEANALYSIS

Te-bearing particles

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TEM

EMPA




TEMIMAGEOFSTEEL&DIFFRACTIONPATTERN

hfp://en.wikipedia.org/wiki/Transmission_electron_microscopy

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TEM

EMPA




BUILDINGANELECTRONMICROSCOPE

CHEM314

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Dunlap,1997

1.  Vacuum2.  ElectrongeneraAon3.  ElectronbeamcondiAoning4.  Electron-sampleinteracAons5.  DetecAon

ELECTRONMICROSCOPE

VACUUMElectron-airinteracAonsshortensthefilamentlifeAme

OperaKngpressure10-4-10-6torr(10-7-10-9atm)

Vacuumsystems

1.Roughingpump:760à10-3torr(1atmà10-6atm)

Removes99.9%airmoleculesmechanically

2.Highvacuumpump

Oildiffusionpump

Turbomolecularpump

Iongeferpump

cryopump

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ELECTRONGENERATIONElectronspersuadedtoleavehome:-HeaKng-Strongelectricfield

1.   Filamentheatedto2000-2700Ktoliberateelectrons.

2.   GridcapisbiasednegaKvely,causingelectronstofocusorconvergeatcrossoverpoint.

3.   ElectronsthenacceleratedtowardanodebymaintainingahighposiKvepotenKal

CONTROLLINGELECTRONBEAMGENERATIONAcceleraKngVoltage(betweengridcapandanode)Highervoltage=higherresoluAonandmoreheatonsample

=deepere-penetraAonandalargerdiameterspot

Bio~10keV;non-bio~20keV

BeamCurrentIncreasedcurrent=moree-hiungsample

=moreheatgeneratedatsample

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Dunlap,1997

CONDITIONINGANDCONTROLLINGTHEELECTRONBEAM

ELECTRONS

SAMPLE

Goal:Directafocusedbeamofelectronsontothesample

Electronscanbemanipulatedby

electromagneAcfields

1.CONDENSERLENSES

Dunlap,1997

ELECTRONS

SAMPLE

Goal:Reducecrossoverspot&sphericalaberraAons

Indiagram,reducedistancebetweenf1andf2

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2.APERTURE

Dunlap,1997

ELECTRONS

SAMPLE

hfp://www.shortcourses.com/use/using1-9.html

Goal:ReducesphericalaberraAonsMakebeamround

TradebetweenresoluAonandelectronthroughput

Alsocontrolsdepthoffield

3.ASTIGMATISMCOILS

Dunlap,1997

ELECTRONS

SAMPLE

hfp://www.intechopen.com/source/html/8670/media/image11.jpeg

Goal:ReducesphericalaberraAonsMakebeamround

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4.RASTERCOILSSteerstheelectronbeamacrosssample

Dunlap,1997

ELECTRONS

SAMPLE

hfp://www.smtcorp.com/scanning-electron-microscopy

SEMRESOLUTION&S:NCONTROLSResoluKonRaAobetweenimagereadoutanddimensionsofscanareaSizeofelectronbeam(funcAonofsource,condenserlensesandaperture)Depthoffield

S:NScanspeedThroughput(aperture,current,voltage)

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SAMPLEPREPARATION-SPUTTERCOATING

hfp://www.mafer.org.uk/tem/electron_atom_interacAon/x-ray_and_auger.htm

ELECTRONSIMPACTINGSAMPLEPrimaryelectrons-Incomingelectronbeam

Tear-drop-shapedexcitaKonvolume

Volumedependson:

1.   Energyandspotsizeofelectronbeam

2.   DensityandelementalcomposiKon

3.   Topography

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POTENTIALELECTRON-SAMPLEINTERACTIONS1.   Backscageredelectrons

2.   Secondaryelectrons

3.   Fluorescentx-rays

4.   Augerelectrons

5.   Cathodeluminescence

6.   Specimencurrent

7.   Transmigedelectrons

8.   Scagering

POSSIBLEOUTCOMESOFELECTRON-SAMPLEINTERACTIONS1.   Backscageredelectrons







8.   Scagering

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Prim

aryElectron

s

BACKSCATTEREDELECTRONS(BSE)Backscageredelectrons:PrimaryelectronsarescaferedoffthesampleatahighangleandwithhighenergyInformaKonProvided:topographicandrelaAvedensity

Sample

BackscaferedElectron(BSE)detector

BackscaferedElectrons

hfp://deben.co.uk/products/ked-products/solid-state-scafered-detector/

100µm

BSE

SECONDARYELECTRONS(SE)Secondaryelectrons:MostprobableeventPrimaryelectrondislodgesasamplevalanceelectronsecondaryelectronsareonlyobservedfromthesurfaceandhaveaverylowenergyDetectedatalowanglefromthesample

InformaKonProvided:highresoluAon,topographicinformaAon

Dunlap,1997

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Dunlap,1997

EFFECTSOFTOPOGRAPHY








8.   Scagering

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31,814eV

Incomingelectron

KLMnucleus

Ejectedelectron

K-edge

4,341eV

L-edgee-

e-

Core-holefilled

Remainingenergydissipatedby1.  X-rayfluorescence2.  AugerelectronejecAon

EJECTIONOFCOREELECTRON

X-RAYSFLUORESCENCEX-rayfluorescence:Primaryelectronknocksoutatomiccoreelectron.Anothercoreelectronfillsthevacantcorehole.AddiAonalenergyreleasedfromatombyX-rayemission

InformaKonProvided:ElementalcomposiAon

Energy(keV)

Fluo

rescen

cecou

nts

As

Fe

105 15

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DETECTINGX-RAYFLUORESCENCEEnergyDispersive-allelementsmeasuredsimultaneouslypoorenergyresoluAon(peakoverlapaproblem)

WavelengthDispersive-elementsmustbemeasuredindividuallyExcellentenergyresoluAon

EnergyDispersiveResoluAon~100eV

WavelengthDispersiveResoluAon~100eV

Wavelength Dispersive Detectors

Showmovie

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GASFLOWDETECTOR

DETECTEDX-RAYSBremstrallungor“breakingradiaKon”-electronsimpingonsampleandcollidewithatoms,losingenergyandgeneraAngx-rays.

Energy(keV)

Fluo

rescen

cecou

nts

As

Fe

105 15

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EJECTIONOFAUGERELECTRONVSFLUORESCENTX-RAY

hfp://en.wikipedia.org/wiki/Auger_electron_spectroscopy

AUGERELECTRONSAugerelectrons:primaryelectronknocksoutatomiccoreelectron.AnothercoreelectronfillsthevacantcoreholeAddiAonalenergyreleasedfromatombyreleaseofAugerelectronAugerelectronsonlyescapefromthesurface

InformaKonProvided:elementalcomposiAon

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8.   Scagering



TEM

EMPA




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TRANSMISSIONELECTRONMICROSCOPY

hfp://en.wikipedia.org/wiki/Transmission_electron_microscopy

SUMMARYOFSEM,EMPA,TEMUSES

Technique OpAcal SEM EMPA TEM

MagnificaAon 2000 150x10320-40x103@UAF

70-100x103@UAF 50x106

ResoluAon 200nm ~10nm 0.5nm

Samplethickness -- -- -- 100nmbiosamples

Beamsize 100snm 20-30µm@UAF <10nm <1nm

hfp://www.ivyroses.com/Biology/Techniques/light-microscope-vs-electron-microscope.php

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TORECORDDURINGYOUREXPERIMENT4SEMTIME

BesureyouhaveaplanofwhatyouwanttoimagewhenyougetSEMKme.

THINGSTORECORD

Whatsampleyou’relookingat,andwhereonyoursampleyou’relooking

AcceleraKngvoltage

Beamcurrent

MagnificaKon

LOOKINGAHEADMonday(Feb22)-Electronmicroscopy

Tuesday/Thursday(Feb23,25)-Experiment3-ColorsandCalories

DueTuesday:Experiment2Report

DueThursday:Experiment5Procedure

Monday(Feb29)-X-raytechniquesDue:Experiment1Report?

2/22/16

34

RESOURCEShgps://www.youtube.com/watch?v=VWxYsZPtTsI

Dunlap,1997

1.  Vacuum2.  ElectrongeneraAon3.  ElectronbeamcondiAoning4.  Electron-sampleinteracAons5.  DetecAon

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ELECTRONMICROSCOPE

2/22/16

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Dunlap,1997

Documents

LEARNING CHECK - Instrumental Analysis · Transmission Electron Microscopy (TEM ... hfp:// SEM POLLENS 2/22/16 10 SEM IMAGES ... - X-ray techniques