Spot the Difference Find the 10 differences between the two pictures.
http://www.saizeriya.co.jp/entertainment/
This is what you might get.
93.4
93.5
93.6
93.7
93.8
93.9
94
94.1
94.2
94.3
0
50
100
150
200
0 50 100 150 200 250 300 350 400 450 500 550 600
Inte
nsi
ty n
orm
aliz
ed b
y Ip
(ar
b. u
nit
s)
Kinetic energy (eV)
What do you do next?
Co
un
ts p
er s
ec.
Photoelectron counts
I0 (p)
Ie
Do not worry!
Ctrl+Q program Based on Windows Excel
Press To analyze all data
Necessary for you to publish Tier 1 journals
Electron energy in atom and solid
• Hydrogen electron energy
– Pauli exclusion principle
– Heisenberg uncertainty principle
– 1 Rydberg = 13.6 eV
• Z > 1
– Hartree-Fock algorithm
– Stationary state: DE=0, Dt=
– Semi-classical spin-orbit effect
– Standard database for each Z
+
e-
+
e-
+ +
10
100
1,000
10,000
100,000
1 10 100
Bin
gdin
g e
ne
rgy
(eV
)
Atomic number
BE vs atomic number
1s
2s
2p1/2
2p3/2
3s
3p1/2
3p3/2
3d3/2
3d5/2
4s
4p1/2
4p3/2
4d3/2
4d5/2
4f5/2
4f7/2
5s
5p1/2
5p3/2
5d3/2
C, N, O
Ta,W
,Au
Spectral distributions
Delta function
Gaussian Lorentzian
Instrumental broadening Thermal (Doppler) broadening
Lifetime broadening Collision broadening
Voigt
FWHM 1/ (lifetime: )
Amplitude
FWHM
Amplitude 1/
energy 0 0 0
2
2
0
2exp
2
1
xxy 2
01
11
xxy
1
0,0
0,
dxx
x
xx
Secondary electron background (inelastic scattering)
S/N √amplitude
Dark current
SE background
Auger/plasmon excitations
Collective electron excitations (plasmon)
Auger process
Auger electron
Photoelectron
X-ray /electron
Electron hole relaxation by photo-absorption 1. Auger emission 2. Fluorescence emission
Spectrum Auger process Core excitation
/ionization
Auger yield(CFS) Valence band yield (ARPES)
Total electron yield
Kinetic energy
Core-level photoemission yield (CIS)
BEPES ≈ KEAES
# photons ≈ # electrons
3 basic background functions
1. Shirley’s BG 2. Touggard’s BG 3. Spline (poly/linear/constant)
Au4f7/2
Au4f5/2
74 76 78 80 82 84 86 88 90 92 94 96 98 100
Binding energy (eV)
Linear BG model
Kinetic energy
Survey-scan analysis
C1s C2p
O1s
O2s O2p
In3d3/2
In3d5/2
In4s
In4p In4d
Sn3d3/2
Sn3d5/2
Sn4s
Sn4p Sn4d
CKLL
OKLL1
OKLL2
InMNN1
InMNN2 InMNN3 InMNN4 InMNN5
SnMNN1
SnMNN3
0
50
100
150
200
-50 0 50 100 150 200 250 300 350 400 450 500 550 600
Inte
nsi
ty n
orm
aliz
ed b
y Ip
(ar
b. u
nit
s)
Binding energy (eV)
1. Normalize intensity by I0. 2. KE to BE by PE=KE+BE+WF. 3. BE calibration by std peak. 4. Identify peak elements. 5. Go to narrow scan.
Orbital dependence p (l=1) s (l=0) d (l=2)
f (l=3)
j=1/2
j=3/2 j=3/2
j=5/2
j=5/2 j=7/2
Spin-orbit splitting Z or dV/dr
Ij=1/2 = 2(1/2) + 1 = 2
Ij=3/2 = 2(3/2) + 1 = 4 1:2
j=1/2
j=3/2
j = l s
Ij = 2j + 1
Example No. 1
ACS Appl. Mater. Interfaces 6, 22051 (2014).
4f (l = 3) j = 7/2, 5/2 I7/2:I5/2 = 4:3
Spin-orbit splitting in Pt 4f : 3.3 eV
Example No. 2
0
10
20
30
40
50
60
97 98 99 100 101 102 103 104 105 106 107
Inte
nsi
ty n
orm
aliz
ed b
y Ip
(ar
b. u
nit
s)
Binding energy (eV)
Emission angle dependence of SiO/Si 2p peaks
20 deg.
30 deg.
40 deg.
50 deg.
60 deg.
70 deg.
The same mean free path
Si2p3/2
Si2p1/2
Si2O SiO
Si2O3
SiO2
97 98 99 100 101 102 103 104 105 106 107
Binding energy (eV)
Emission angles
Thickness: 3Å
2p (l = 1) j = 3/2, 1/2 I3/2:I1/2 = 2:1
20
70
Chemical shifts on surface
http://www.all-nano.waseda.ac.jp/ coe2001/ohdomari/7.html
Which software?
PHI MultiPak
Spectral Data Processor
Dr. Roger Nix (Univ. London) Free for academic use only
XPSPEAK (free)
55K THB
35K THB
58K THB
20K THB
Which system you used?
Thermo CLAM2 NI LabVIEW
VG Scienta R4000 VG Scienta SES
PHI VersaProbe II PHI MultiPak
SUT-NANOTEC-SLRI
ULVAC-PHI MultiPak Licensed SLRI PC only Optimized for x-ray anode XPS machine
https://www.phi.com/surface-analysis-equipment/versaprobe.html
Wave Metrics Igor Pro
http://www.wavemetrics.com
595 USD (academic: 435 USD) It costs about 20,000 THB.
1. VG Scienta code • Load Spectrum • Reduce Dimension • Background … • Curve Fit … 2. Igor Pro XOP
Multi-peak Fit ver. 2
Microsoft Office Excel Available in almost every PCs Working slow for solver curve fit
Visual Basic Application codes + Solver for curve fit
1. eXPFit by Dr. Roger Nix (Univ. London) 2. Ctrl+Q by Dr. Hideki NAKAJIMA (SLRI)
optimized for SR-based XPS/XAS with database
It accepts BE scale only. No database available.
XPS, XAS & AES on Carbon
XAS: Scanned PE Measured: TEY
XPS: Fixed PE Measured: KE (BE) of each electron
Pico-amps meter
i : TEY
XPS, AES
XAS