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
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
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
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
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).
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
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 – Ωf – k
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
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
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
45º45º
Secondary Target (Z!!)
SR
Monochromator
Sample
Detector
45º
45º
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 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
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
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
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
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]
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
RR
S c
ross s
ectio
n [cm2/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)
2200 ),(
),(
KSLK
SS
S
S
E
EEEG
dE
EEd
WW
)( xB
Ay
MC Valentinuzzi et al., X-Ray Spectrometry 37, 555-560 (2008).
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
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).
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-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!
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
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)
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
Inte
nsi
ty [a
.u.]
Energy [keV]
Mn(0.99)-Fe(0.01)
Primary Fluorescence
Total Raman
Enhancement
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
Inte
nsity
[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
Inte
nsity
[a.u
.]
Energy [keV]
Ti(0.9999)-V(0.0001)
Primary Fluorescence
Total Raman
Secondary Fluorescence
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
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
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
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.
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
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.
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 ]
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.
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
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
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.
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
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
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
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
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
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
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
0
50
100
150
Inte
nsity [cts
]
Energy [eV]
AsIII
AsV
MMAsV
DNAsV
RRS residuals of the different arsenic species.
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
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
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
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
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
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
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)
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.
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
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).
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
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
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