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Joint ICTP-IAEA School on Novel Experimental Methodologies for Synchrotron Radiation Applications in Nano-science and Environmental Monitoring 17 November - 28 November 2014 Hctor Jorge Snchez Joint ICTP-IAEA School on Novel Experimental

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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

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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

Matter Incoherent Scattering Compton Electron Compton Photon Coherent Scattering Rayleigh Photon Primary Photon

µ = c + i + 

Photoelectric Effect Auger Electron Fluorescent Photon Photoelectron

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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

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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

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

1 2 ´) ( 2 2 1 1 , 2

´ 2 ~ cos ´´) ( ´) ( 1 ln ´) ( cos cos ´´) ( ) ~ ( 1 ln ´´) ( cos ´) ( ) ~ ( ´) ´´, ( ´´) , ~ ( ) ~ ( 8

E N k E E E s s s s s s s s y i x k y x i

dE e E d E E E E E E G E E E E Q E E Q E I I               

           

 

max max 2 2

2 ´) ( 1

´ 2 ~ ´) ( ) ~ ( ´) , ~ ( ) ~ ( 4

E E E E s s x i x i

dE e E d G E E E E Q E I I     

  • J. Sherman, Spectrochim. Acta 7, 283 (1955).
  • T. Shiraiwa and N. Fujino, Jpn. J. Appl. Phys. 5, 886 (1966).
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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

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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

K L1 L2 L3 . . . hn < WK

hnRRS

Wf

hnRRS = hn – ΩL2

L2 – Ωf – k

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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

   

   W                     

3 3 2 2 2 2

8 ) ( 1 ) , (    k d u E E M n c mc e E E dE E E d

L k s fi k S S S  

Kramers- Heisenberg ´s Equations (Time Depending Perturbation Theory) ) (

1 2 K k k fi

i u E m S u p k S u p P M   W         

 

2 2

) , ( ) , (

K S L K S S S S

E E E E G dE E E d    W  W  

 

 W   

 W  W  

f L e

E E E L K

dE E E E E

2 2 1

2 ) ( 2 1

e ) , (

) , (

S

E E d

S

E ) , (

1 0 E

E 

1

E

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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

X-Ray Tube Primary Target Detector

45º 45º

Secondary Target (Z!!) SR Monochromator Sample Detector

45º 45º

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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

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 T
  • rr in a standard

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

Storage Ring

Synchrotron Radiation Incident Beam Sample Holder First Slits X-Ray Eye Monochromator Second Slits Solid State Detector

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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 7000 7500 8000 8500 9000 9500 10000 200 400 600 800 1000 1200

Intensity (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

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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

K S F R F R F

G I I G R E I I E    ) / 1 1 )( ( ) (  

 

) ( ) ( e 1

2 ) ( ) ( 2 F d E E F

E E G

F

 

  

  

 

6200 6300 6400 6500 6600 6700 6800 6900 7000 7100 0,0 0,2 0,4 0,6 0,8 1,0

RRS cross section [cm

2/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

RRS cross section [cm

2/g]

Energy [eV]

Measured KL-RRS cross section for Cu (points) and a non-linear fitting to an expression with the functional form of the theoretical cross section (solid line)

8700 8800 8900 9000 9100 9200 9300 9400 9500 9600 9700 0,0 0,2 0,4 0,6 0,8 1,0

RRS cross section [cm

2/g]

Energy [eV]

Measured KL-RRS cross section for Zn (points) and a non-linear fitting to an expression with the functional form of the theoretical cross section (solid line)  

2 2

) , ( ) , (

K S L K S S S S

E E E E G dE E E d    W  W   ) ( x B A y  

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

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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

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

1 2 ´) ( 2 2 1 1 , 2

´ 2 ~ cos ´´) ( ´) ( 1 ln ´) ( cos cos ´´) ( ) ~ ( 1 ln ´´) ( cos ´) ( ) ~ ( ´) ´´, ( ´´) , ~ ( ) ~ ( 8

E N k E E E s s s s s s s s y i x k y x i

dE e E d E E E E E E G E E E E Q E E Q E I I               

           

 

max max 2 2

2 ´) ( 1

´ 2 ~ ´) ( ) ~ ( ´) , ~ ( ) ~ ( 4

E E E E s s x i x i

dE e E d G E E E E Q E I I     

  • J. Sherman, Spectrochim. Acta 7, 283 (1955).
  • T. Shiraiwa and N. Fujino, Jpn. J. Appl. Phys. 5, 886 (1966).
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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 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-K Cu-K Ni-K Fe-K Intensity [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

Intensity [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

  • f 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

Intensity [a.u.] Energy [keV] Measured Spectrum Al KLine 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!

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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

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 Intensity [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 Intensity [a.u.] Energy [keV] Mn(0.0001)-Fe(0.9999) Primary Fluorescence 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 Intensity [a.u.] Energy [keV] Mn(0.99)-Fe(0.01) Primary Fluorescence Total Raman Enhancement

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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

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 Intensity [a.u.] Energy [keV] Ti (0.99)-V(0.01) Primary Fluorescence 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 Intensity [a.u.] Energy [keV] Ti(0.9999)-V(0.0001) Primary Fluorescence Total Raman Secondary Fluorescence

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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

K L1 L2 L3 . . . hn < WK

hnRRS

Wf

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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

Storage Ring

Synchrotron Radiation Incident Beam Sample Holder First Slits X-Ray Eye Monochromator Second Slits Solid State Detecto r Leani, J., Sánchez, H.J., Pérez C. J. Anal.At. Spectrom., (2010), DOI:10.1039/c0ja00046a

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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

KL-RRS spectrum obtained for a Fe sample with incident energy of 7022 eV. Solid lines represent data fitting.

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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

Fe, FeO, Fe3O4 and Fe2O3 residuals of the experimental Raman

  • spectra. Incident energy
  • f 7022 eV.

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

Fe FeO Fe3O4 Fe2O3 Intensity [a.u.] Energy [KeV]

4800 4950 5100 5250 5400 5550 5700

Intensity [a.u.] Energy [eV]

Mn2O3 Mn

Mn, and Mn2O3 residuals

  • f the experimental

Raman spectra. Incident energy of 6450 eV.

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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

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 ]

Fe2O3 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.

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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

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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

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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

RRS residuals of Cu-oxide standards (a) and a stratified sample (b)-(e). Confocal volumen  90μm.

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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

Polycapillary Polycapillary Sample

µXRF Station of D09B Beamline (LNLS)

Crown Section Root Section

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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

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 Intensity [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 Intensity [a.u.] Energy [KeV]

Crown Section Root Section

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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

Sample

Detector 90° Incident Beam

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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

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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

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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 9500 10000 10500

  • 150
  • 100
  • 50

50 100 150

Intensity [cts] Energy [eV] AsIII AsV MMAsV DNAsV

RRS residuals of the different arsenic species.

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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

Sample

Detector 90° Incident Beam Incident Beam Incident Beam

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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

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

  • xidized 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

  • xidized sheet of copper

at different depths

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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

5600 5700 5800 5900 6000 6100 6200

Intensity [a.u.] Energy [eV]

~ 10 nm Fe 200°C

5600 5700 5800 5900 6000 6100 6200

Intensity [a.u.] Energy [eV]

5600 5700 5800 5900 6000 6100 6200

Intensity [a.u.] Energy [eV]

~ 100 μm Fe foil ~ 10 nm Fe (200°C) ~ 200 nm Fe (20°C) Fe(II) oxide Fe(III)

  • xide

Pure 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 [°]

Fe3O4 Fe2O3 Fe

Depth [nm]

2

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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

Preparing for data treatment

Intensity [cts] Energy [eV] Energy [eV] Intensity [cts] Energy [eV] Normalizaed Intensity Data set Matrix of n spectra (samples) × p variables (channels)

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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

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.

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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

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

  • rder 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”

  • xidized 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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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

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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

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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