Joint ICTP-IAEA School on Novel Experimental Methodologies ...indico.ictp.it/event/a13226/session/5/contribution/... · Joint ICTP-IAEA School on Novel Experimental Methodologies

Héctor Jorge Sánchez

Joint ICTP-IAEA School on Novel Experimental Methodologies for Synchrotron Radiation Applications in

Nano-science and Environmental Monitoring - 17 November - 28 November 2014

Joint ICTP-IAEA School on

Novel Experimental Methodologies for Synchrotron Radiation

Applications in Nano-science and Environmental Monitoring

17 November - 28 November 2014




Matter

Incoherent Scattering

Compton

Electron

Compton

Photon

Coherent Scattering

Rayleigh

Photon

Primary

Photon

µ = c + i +

Photoelectric Effect

Auger

Electron

Fluorescent

Photon

Photoelectron







1 f

ip I

1 , 1 i c s I

2 f

ip I

2 , 2 i c s I

) ( ' E I

i c s I ,

Sample

Reflector

2

max

max

2

2

0

1

0

2

)́(

2

2

1

10,2 ´2

~

cos´´)(

´)(1ln

´)(

cos

cos´´)(

)~

(1ln

´´)(

cos

´)()~

(

´)´´,(´´),~

()~

(

8

E

N

k

EEE

s

s

ss

s

sss

y

i

x

kyx

i dEe

EdE

E

EE

E

EGEE

EEQEEQEII

max

max

2

2

00

2

)́(

01 ´2

~

´)()~

(

´),~

()~

(

4

EE

EE

ss

x

ix

i dEe

EdGEE

EEQEII

J. Sherman, Spectrochim. Acta 7, 283 (1955).

T. Shiraiwa and N. Fujino, Jpn. J. Appl. Phys. 5, 886 (1966).







K

L1

L2

L3

...

hn < WK

hnRRS

Wf

hnRRS = hn – ΩL2 – Ωf – k




W

3

3

0

22

2

2

0

0

8

)( 1),(

kduEEMnc

mc

e

E

E

dE

EEd LksfikS

S

SKramers- Heisenberg ´s Equations

(Time Depending Perturbation Theory)

)( 0

12

Kkk

fiiuEm

SupkSupPM

W

2200 ),(

),(

KSLK

SS

S

S

E

EEEG

dE

EEd

WW

W

WW

fL eE EE

LK

dEE

EEE

0

2

21

0

2

)(

210 e ),(

),( 0 SEEd

SE

),( 10 EE

1E




X-Ray Tube

Primary Target

Detector

45º45º

Secondary Target (Z!!)

SR

Monochromator

Sample

Detector

45º

45º




XRF Beamline (LNLS)

• Storage ring operating at 3.7 GeV and nominal current of 100 mA.

• Silicon (111) channel-cut double-crystal monochromator.The energy resolution is 3×10−4 between 7

and 10 keV.

• A motorized computer-controlled set of vertical and horizontal slits to limit the beam size, before and

after the monochromator.

• A ionization chamber to measure the primary beam intensity.

• A Si(Li) solid state detector, with a resolution of 165 eV at 5.9 keV.

• The samples were mounted in a vacuum chamber with a sample holder at 10−2 Torr in a standard

geometrical configuration of 45◦ of incident and take-off angles.

Storage Ring

Synchrotron

RadiationIncident

Beam

Sample

Holder

First

Slits

X-Ray Eye

Monochromator

Second

Slits

Solid State

Detector




7000 7500 8000 8500 9000 9500 10000

0

200

400

600

800

1000

1200

Inte

nsity

(a.u

.)

Energy [eV]

KL-RRS spectrum of Zn obtained with incident energy of

9594 eV. Solid lines represent the data fitting of each peak.

Sánchez, H.J. et al. J Phys B: At Mol Opt Pys 2006; 39: 1-11h

LNLS,

D09B Beamline

Channel Cut

monochromator.

Si(Li) Detector




K

SF

R

FR

F

GII

GREIIE

)/11)(( )(

0

00

0

)()(

e1

0

2

)()(2 0

F

dEE

FEE

G

F

6200 6300 6400 6500 6600 6700 6800 6900 7000 7100

0,0

0,2

0,4

0,6

0,8

1,0

RR

S c

ross s

ection [

cm2/g

]

Energy [eV]

Measured KL-RRS cross section for

Fe (points) and a non-linear fitting

to an expression with the

functional form of the theoretical

cross section (solid line)

8100 8200 8300 8400 8500 8600 8700 8800 8900 9000

0,0

0,2

0,4

0,6

0,8

1,0

RR

S c

ross s

ection [

cm2/g

]

Energy [eV]


Cu (points) and a non-linear fitting




8700 8800 8900 9000 9100 9200 9300 9400 9500 9600 9700

0,0

0,2

0,4

0,6

0,8

1,0

RR

S c

ross s

ectio

n [cm2/g

]

Energy [eV]


Zn (points) and a non-linear fitting




2200 ),(

),(

KSLK

SS

S

S

E

EEEG

dE

EEd

WW

)( xB

Ay

MC Valentinuzzi et al., X-Ray Spectrometry 37, 555-560 (2008).




1 f

ip I

1 , 1 i c s I

2 f

ip I

2 , 2 i c s I

) ( ' E I

i c s I ,

Sample

Reflector

2

max

max

2

2

0

1

0

2

)́(

2

2

1

10,2 ´2

~

cos´´)(

´)(1ln

´)(

cos

cos´´)(

)~

(1ln

´´)(

cos

´)()~

(

´)´´,(´´),~

()~

(

8

E

N

k

EEE

s

s

ss

s

sss

y

i

x

kyx

i dEe

EdE

E

EE

E

EGEE

EEQEEQEII

max

max

2

2

00

2

)́(

01 ´2

~

´)()~

(

´),~

()~

(

4

EE

EE

ss

x

ix

i dEe

EdGEE

EEQEII

J. Sherman, Spectrochim. Acta 7, 283 (1955).

T. Shiraiwa and N. Fujino, Jpn. J. Appl. Phys. 5, 886 (1966).




3 4 5 6 7 8 9 10 11

1E-13

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

1E-6 Zn-KCu-K

Ni-K

Fe-K

Inte

nsity [u

.a.]

Energy [keV]

Fluorescent

Coherent

Incoherent

Raman

Mn-K

Calculated spectrum of

a metal alloy irradiated

with an Mo x-ray tube

@45 kV

1,0 1,2 1,4 1,6 1,8 2,0 2,2

1E-9

1E-8

1E-7

Inte

nsity [a

.u.]

Energy [keV]

Bkg Total

Bkg Raman

Bkg Incoh

Bkg Coh

Calculated spectrum of

Si (0.9995) with Al

impurities (0.0005)

irradiated with

monochromatic photons

of 1739 eV

1,0 1,2 1,4 1,6 1,8 2,0

0,0

5,0x10-8

1,0x10-7

1,5x10-7

2,0x10-7

Inte

nsity [a

.u.]

Energy [keV]

Measured Spectrum

Al KLine

Total Bkg

Raman Bkg

Analysis of impurities in silicon wafers by TXRF. The combination of VPD method and SR

allows DL of 107 at/cm2. For Al impurities, Raman peak has to be considered!




Binary samples with proximate atomic numbers.

The Raman background competes with secondary fluorescence

Mo X-ray tube @45 kV.

Detector of 150 eV.

5,0 5,5 6,0 6,5 7,0 7,5

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

1E-6

Inte

nsity

[a.u

.]

Energy [keV]

Mn(0.01)-Fe(0.99)

Primary Fluorescence

Total Raman

Enhancement Mn Fe

5,0 5,5 6,0 6,5 7,0 7,5

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

1E-6

Inte

nsity

[a.u

.]

Energy [keV]

Mn(0.0001)-Fe(0.9999)


Total Raman

Enhancement

5,0 5,5 6,0 6,5 7,0 7,5

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

1E-6

Inte

nsi

ty [a

.u.]

Energy [keV]

Mn(0.99)-Fe(0.01)


Total Raman

Enhancement




Binary samples with proximate atomic numbers.

The Raman background competes with secondary fluorescence

Mo X-ray tube @45 kV.

Detector of 150 eV.

Ti V

3,5 4,0 4,5 5,0 5,5 6,0

1E-13

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

Inte

nsity

[a.u

.]

Energy [keV]

Ti (0.99)-V(0.01)


Total Raman

Secondary Fluorescence

3,5 4,0 4,5 5,0 5,5 6,0

1E-13

1E-12

1E-11

1E-10

1E-9

1E-8

1E-7

Inte

nsity

[a.u

.]

Energy [keV]

Ti(0.9999)-V(0.0001)


Total Raman

Secondary Fluorescence




K

L1

L2

L3

...

hn < WK

hnRRS

Wf




Storage Ring

Synchrotron

RadiationIncident

Beam

Sample

Holder

First

Slits

X-Ray Eye

Monochromator

Second

Slits

Solid

State

Detecto

rLeani, J., Sánchez, H.J., Pérez C. J. Anal.At. Spectrom., (2010), DOI:10.1039/c0ja00046a




KL-RRS spectrum obtained

for a Fe sample with incident

energy of 7022 eV.

Solid lines represent data

fitting.




Fe, FeO, Fe3O4 and

Fe2O3 residuals of the

experimental Raman

spectra. Incident energy

of 7022 eV.

5,6 5,7 5,8 5,9 6,0 6,1 6,2

Fe

FeO

Fe3O

4

Fe2O

3

Inte

nsity [a

.u.]

Energy [KeV]

4800 4950 5100 5250 5400 5550 5700

Inte

nsity

[a.u

.]

Energy [eV]

Mn2O3

Mn

Mn, and Mn2O3 residuals

of the experimental

Raman spectra. Incident

energy of 6450 eV.




4800 4900 5000 5100 5200 5300 5400 5500 5600 5700

R a m a n E X A F S

E n e r g y [ e V ]

M n 2 O

3

M n O 2

M n

6800 7000 7200 7400 7600 7800

R a m a n E X A F S

E n e r g y [ e V ]

C u O

C u 2 O

C u

5600 5700 5800 5900 6000 6100 6200

E n e r g y [ e V ]

Fe2O

3

Fe

Figures show the comparison between RRS residuals and EXAFS patterns, after data processing, for:

(a) Mn compounds, (b) Fe samples, and (c) Cu species.










RRS residuals of Cu-oxide standards (a) and a stratified sample (b)-(e). Confocal volumen

90μm.




Polycapillary

Polycapillary

Sample

µXRF Station of D09B Beamline (LNLS)Crown Section Root Section




3.48 3.50 3.52 3.54 3.56 3.58 3.60 3.62 3.64 3.66 3.68

Dentine 1

Dentine 2

Enamel 1

Enamel 2

Inte

nsity

[a.u

.]

Energy [KeV]

3,48 3,50 3,52 3,54 3,56 3,58 3,60 3,62 3,64 3,66 3,68

Dentine 1

Dentine 2

Cement

Calculus

Inte

nsity

[a.u

.]

Energy [KeV]

Crown Section Root Section




Sample

Detector

90°Incident Beam










9500 10000 10500

-150

-100

-50

0

50

100

150

Inte

nsity [cts

]

Energy [eV]

AsIII

AsV

MMAsV

DNAsV

RRS residuals of the different arsenic species.




Sample

Detector

90°Incident Beam

Incident Beam

Incident Beam




5600 5700 5800 5900 6000 6100 6200

Observed

depth [nm]

1.74

1.77

Energy [eV]

870

429

133

2.05

1.83

1.73

RRS residuals of an

oxidized sheet of iron at

different depths

6800 6900 7000 7100 7200 7300 7400 7500 7600 7700 7800

22840

629

576

522

467

411

354

Energy [eV]

Observed

depth [nm]

RRS residuals of an

oxidized sheet of copper

at different depths




5600 5700 5800 5900 6000 6100 6200

Inte

nsity [a

.u.]

Energy [eV]

~ 10 nm Fe 200°C

5600 5700 5800 5900 6000 6100 6200

Inte

nsity [a

.u.]

Energy [eV]

5600 5700 5800 5900 6000 6100 6200

Inte

nsity [a

.u.]

Energy [eV]

~ 100 μm Fe foil

~ 10 nm Fe (200°C)

~ 200 nm Fe (20°C)

Fe(II) oxide

Fe(III)

oxidePure Fe

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

1

10

100

Incident Radiation Angle [°]

Fe3O

4

Fe2O

3

Fe

De

pth

[n

m]

2




Preparing for data treatment

Inte

nsi

ty[c

ts]

Energy [eV]

Energy [eV]

Inte

nsi

ty[c

ts]

Energy [eV]

Norm

aliz

aed

Inte

nsi

ty

Data set

Matrix of n spectra (samples) × p variables (channels)




RRS residual spectra of the different arsenic species.

Water contaminated with different species of arsenic

deposited on a silicon wafer.

PCA results of the different samples (PC1 vs PC2).

Water contaminated with different species of arsenic

deposited on a silicon wafer.

An PCA was performed over the selected energies correlation

matrix of the processed spectra, and spectra were represented in

the PC1-PC2 plane.




Surface nanolayers of Cu and Cr on a silicon

wafer.

A Ward cluster analysis, with Euclidean distance, was

performed on the data of the processed spectra

corresponding to Cr and Cu “in situ” oxidation in

order to identify different groups in the complete set of

spectra. An PCA was performed over the selected

energies correlation matrix of the processed spectra,

and spectra were represented in the PC1-PC2 plane.

Dendogram obtained from the Cluster Analysis

performed on the 30 spectra of the Cu “in situ”

oxidized sample.

CP1-CP2 plane obtained from the PCA applied to

the Cu “in situ” oxidized sample. This plane

comprises 39,4% of the total variance of the data

set. Blue spectra belong to non oxidized state,

while red spectra belong to oxidized state.

PC1-PC2 plane obtained from the PCA applied to

the Cr Multilayer oxidized sample. This plane

comprises a 55,6% of the data set’s total variance.

Blue spectra belong to the first layer of Cr2O3

while red spectra belong to second layer (CrO).










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Joint ICTP-IAEA School on Novel Experimental Methodologies ...indico.ictp.it/event/a13226/session/5/contribution/... · Joint ICTP-IAEA School on Novel Experimental Methodologies