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S. Tanuma, C. J. Powell*, D. R. Penn*, and K. Goto**
National Institute for Materials Science (NIMS)
*National Institute of Standards and Technology (NIST)
**National Institute of Advanced Industrial Science and Technology
Technology Chubu
1. Introduction
2. Calculation of IMFPs from optical data
- Evaluation of energy-
energy-loss function data
- Fano Plots - Modified Bethe equation fits
- Comparison with IMFPs from the TPP-
TPP-2M equation
3. Experimental determination of IMFPs
- Results for 13 elemental solids
4. IMFP Applications
- Effective attenuation lengths
- Mean escape depths
- Information depths
- Modeling XPS for Thin-
Thin-Film Structures
5. Summary
1
1
1. Introduction
2
2. Calculation of IMFPs from optical data
Flow of calculation d 2 me02 1 1
Im
dqd N hE (q, ) q
n 1
Experimental optical
data
Im 1/ E IMFPs
: optical constants (ELF) q=0
- function of E
: atomic scattering - check with Sum Rules
factors Penn algorithm
Co
30 1.2 10 0
- energy dependence :
10 -1 cobalt
25 1
optical energy loss function (q
(q = 0)
atomic scattering factor (f1, f2)
-2
10
Energy Loss Function
optical constants (n,k)
- q dependence :
20 0.8
f1
n
f2 10 -3
k
15 0.6
10 -4
Lindhard model dielectric function (RPA)
10 0.4
10 -5
5 0.2 10 -6
single-
single-pole approximation (E
(E > 300 eV)
10 -7
0 0
10 -8
-5 -0.2 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5
10 100 1000 10 4 10 5
E(eV)
Electron Energy (eV)
3
Conditions and materials for IMFP calculations
- 12 organic compounds
26-n-paraffin, adenine, beta-carotene, diphenyl-hexatriene, guanine, kapton,
polyacetylene, poly(butene-1-sulfone), polyethylene, polymethylmethacrylate,
polystyrene, and poly(2-vinylpyridine)
- 21 inorganic compounds
Al2O3, GaAs, GaP, H2O, InAs, InP, InSb, KBr, KCl, LiF, MgO, NaCl, NbC0.712,
NbC0.844, NbC0.93, PbS, SiC, SiO2, VC0.758 , VC0.858 and ZnS.
4
TheIMFPswerecalculatedinthe50eVto30keV
energyrange.
Theywerecalculatedatequalintervals
Theseshowthelistofthecalculatedmaterials.
Wehavecalculatedthese42elementalsolids,12
organiccompoundsand21inorganiccompoundsas
shownhere.
Becausetheyhaveopticalconstantssufficient
energyrange.
4
Evaluations of Energy-Loss Functions with Sum
Rules
f-sum rule (or oscillator-strength sum rule )
E max
Z eff (2 / 2 2p ) E Im[1 / (E )]d (E )
0
When E max
: total number of electrons
Z eff Z for material
Peff 1
5
5
101
Polyethylene
10-1
Energy loss function and sum-rule
10-9 Poly-C2H4
1 10 -11
15
P
0.4 f sum
Nv = 12
Nv
eff
10 (12.3)
Z
0.2
KK-sum error: 0.9 %
0 Nv=12
5
0 1 2 3 4 5
10 10 10 10 10 10 C2H4 (Z=16)
E (eV)
max
0
:saturates over 60 eV 100 101 102 103 104 105
:evaluated low-energy region (and n(0) value gave large contribution) E (eV) 6
max
6
Al and Al2O3: sum rule results
14
1
12
f-sum 0.8 KK-sum
10 Error = 1.7 %
aluminum aluminum
8 0.6
eff
Error = - 0.9 %
eff
P
Z
6 0.4
4
0.2
2
0
0
10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5
10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5
E (eV)
E (eV) max
max
50
1
Al O Al O
2 3
2 3
40
0.8
Error = 0.9 %
30 Error = - 5.3 % 0.6
eff
eff
P
Z
20 0.4
0.2
10
0
0
10 -3
10 -2
10 -1 0
10 10 10 1 2
10 3
10 4
10 5
10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 7
E (eV) E (eV)
max max
7
Sum-rule results for elemental solids and inorganic
compounds
Elements Inorganic compounds
Eelements
40 40
Zr
0 0
-20 -20
Nb Sn InSb
InAs
GaAs
-40 -40
-40 -20 0 20 40
-40 -20 0 20 40
8
Sum-rule results for organic compounds
KK-sum
20
RMS sum-rule error (fi%)
f
Error of KK-sun rule (%)
2
10 rms(%)
i
n
26-n-paraffin
0
Polyacetylene
Average f-sum error: 7.0%
-10
9
Calculated IMFPs for 42 elemental solids
10 2
10 1
10 0
10 1 10 2 10 3 10 4 10 5
Electron Energy (eV)
10
10
Calculated IMFPs for compounds
21 inorganic compounds
10 3 10 3
12 Organic compounds
Inelastic Mean Free Paths()
10 1 10
10 0 1
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
Electron Energy (eV) Electron Energy (eV)
11
11
Modified Bethe equation for IMFP
E
Ep = bulk plasmon energy
E p2 ln E C / E D / E 2 , , C, and D are parameters
12
M. Inokuti, Rev. Mod. Phys. 43, 297 (1971).
12
Analysis of energy dependence of IMFPs by Fano Plots:
50 eV to 30 000 eV
E
()
E p2 ln E C / E D / E 2
Fano plot:
E / vs lnE
E E p2 ln E C E D E 2 (eV/)
C, D -> parameters
For high energies: Fano Plots -> straight line
E E p2 ln E C / E D / E 2 E p2 ln E
13
13
Fano plots for Si and Ru E E p2 ln E C E D E 2
silicon ruthenium
80
calculated IMFPs 120 calculated IMFPs
70
Mod. Bethe Eq. Fit Mod. Bethe Eq. Fit
60 100
Energy/IMFP(eV/)
Energy/IMFP(eV/)
40
60
30
40
20
C D 20 C D
10
0.0311 0.1186 1.104 30.3 0.0186 0.0763 1.484 40.5
0 0
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
Electron Energy (eV) Electron Energy (eV)
14
14
Fano plots for -carotene and polyethylene
60 60
calculated IMFPs calculated IMFPs
50 Mod. Bethe Eq. Fit 50 Mod. Bethe Eq. Fit
Energy/IMFP(eV/)
Energy/IMFP(eV/)
40 RMS = 0.1% 40 RMS = 0.2%
-carotene
30 30
Polyethylene
20 20
10 C D
10 C D
0.0183 0.183 1.16 15.5 0.0188 0.168 1.28 18.5
0 0
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
Electron Energy (eV) Electron Energy (eV)
E E p2 ln E C E D E 2
15
15
Fano plots for Al2O3 and GaAs E E p2 ln E C E D E 2
100 GaAs
60
calculated IMFPs Al O
2 3 calculated IMFPs
Mod. Bethe Eq. Fit
Mod. Bethe Eq. Fit
80 50
Energy/IMFP(eV/)
Energy/IMFP(eV/)
40
60
30
40
20
0 0
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
Electron Energy (eV) Electron Energy (eV)
C D C D
0.0146 0.0815 1.16 31.1 0.0306 0.0469 1.05 53.4
16
16
Results of Modified Bethe equation fits to calculated
IMFPs over the 50 eV to 30,000 eV range
M. Bethe fit to IMFPS of 42 elemental soldis,
Average RMS deviation 20
12 organic and 21 inorganic cpmpounds
elements
organic compounds
42 elemental solids : 0.47 % inorganic compounds
12 organic compounds : 0.12 % 15
Frequency
10
17
17
TPP-2M equation for IMFPs
E
E p2 ln E CE 1 DE 2
0.10 0.944 E p2 E g2
0.5
0.069 0.1
0.191 0.5 M: atomic or molecular weight
C 1.97 0.91U : density
D 53.4 20.8U Nv: number of valence electrons
Nv E p2 Eg: band-gap energy
U
M 829 .4
- original energy range: 50 eV to 2000 eV (now extended to 30 keV)
- based on IMFP data for 27 elemental solids and 14 organic
compounds
18
S. Tanuma, C. J. Powell, and D. R. Penn, Surf. Interface Anal. 21, 165 (1994).
18
Comparison of calculated IMFPs for Si and Ru with TPP-2M
IMFPs
silicon ruthenium
10 3 10 3
calculated IMFPs calculated IMFPs
Mod. Bethe Eq. Fit
Inelastic Mean Free Path()
100 100
10 10
1 1
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
Electron Energy (eV) Electron Energy (eV)
19
19
Comparison of calculated IMFPs for -carotene and
polyethylene with TPP-2M IMFPs
-carotene Polyethylene
100 100
10 10
1
1 10 1 10 2 10 3 10 4
10 1 10 2
10 3
10 4
Electron Energy (eV)
Electron Energy (eV)
RMS = 13.1 % (50 eV to 30,000 eV) RMS = 7.9 % (50 eV to 30,000 eV)
20
20
Comparison of calculated IMFPs for Al2O3 and GaAs with
TPP-2M IMFPs
Al O GaAs
2 3
10 10
1 1
10 1 10 2 10 3 10 4 10 1 10 2 10 3 10 4
Electron Energy (eV)
Electron Energy (eV)
RMS = 14.5 % (50 eV to 30,000 eV) RMS = 37.3 % (50 eV to 30,000 eV)
21
21
RMS differences between calculated IMFPs (from optical energy-loss
functions) and TPP-2M IMFPs over the 50 eV to 30,000 eV energy
range:
elemental solids in organic and organic compounds
RMS differences between calculated IMFPs and TPP-2M IMFPs
Average RMS: 13.3 % (10.3 %) 60 Average RMS: 8.1 % for organic
80
14.3 % for inorganic
50 - 30 000 eV
70 50 - 2,000eV diamond 50 50 - 2000 eV
60 50 - 30,000eV LiF
40
50 GaAs
graphite
40 30
Cs InAs, InSb, InP
30 20
20
10
10
0 0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
3
3
U (mol/cm ) U= Nv /Aw (mol/cm )
22
23
23
Summary (continued)
The optical IMFPs were also compared with IMFPs from the
TPP-2M equation; the average RMS deviations were 13 %
(elements), 8 % (organic compounds) and 14 % (inorganic
compounds) for energies from 50 eV to 30,000 eV.
Relatively large RMS deviations were found for diamond,
graphite, and cesium in the elements group. If these elements
were excluded, the average RMS deviation was 10.3 %. Large
deviations were also found for GaAs and LiF.
We conclude that the TPP-2M equation is useful for IMFP
estimation in other materials for energies up to 30,000 eV with
an average uncertainty of about 11 %.
24
3. Experimental Determination of Electron
Inelastic Mean Free Paths by Elastic-Peak
Electron Spectroscopy (EPES)
assess the reliability of IMFPs calculated from energy-loss
functions with the Penn algorithm (optical IMFPs) and from
the TPP-2M equation.
determine IMFPs for Ag, Au, Cr, Cu, Fe, Ga, C (graphite) ,
Mo, Pt, Si, Ta, W, and Zn over the 50 eV to 5,000 eV energy
range from backscattered elastic-peak intensities (EPIs)
using a Ni reference material.
25
Elastic-peak electron spectroscopy (EPES)
26
Measurements of
Measurements of EPIs
EPIsby
byabsolute
absoluteCMA
CMA
27
Measured elastic -peak intensity ratios (with
elastic-peak
respect to Ni) as a function of electron energy
5 5
4 Au/Ni
Mo/Ni
Cu/Ni
4 4 Ta/Ni
Ga/Ni
W/Ni
3 Si/Ni graphite/Ni Zn/Ni
3 3
2
2 2
1
1 1
0 0 0
100 1000 100 1000 100 1000
Electron energy (eV) Electron energy (eV)
Electron Energy (eV)
Low atomic number : graphite,
silicon
Middle atomic number: Fe, Cr, Zn,
28
Calculation of Elastic -Peak Intensities from Monte
Elastic-Peak
Carlo Simulations
Instrumental function
Ni at 1000 eV
d S
1.4 10 -3
I Gt f s / N 0 exp dS (d /dS)/N
dS 1.2 10 -3
0
0
(d /dS)/N x exp(-S/ )
0
1 10 -3
e-
0
Surface excitation factor
(d /dS)/N
8 10 -4
IMFP
path-length distribution of 6 10 -4
electrons detected by CMA
4 10 -4
(42.3 6)
2 10 -4
S: total path length = s1 +
S2 + S3+ S4 .... 0 10 0
0 20 40 60 80 100 120
Total pathe length ()
S4 S1
:Elastic
Elastic--scattering cross sections from
S2 the Thomas-
Thomas-Fermi-
Fermi-Dirac potential
S3 :Pseudo random number generator
Mersenne Twister
29
29
Calculation of Elastic -Peak Intensity Ratio to Ni Reference
Elastic-Peak
d dS / N
exp S x dS
x
I x
x
0
Ni
0
d dS / N
I cal Ni Ni
exp S Ni dS
0
0
Then, I x I x
2
Ni Ni min
I mesaured I cal
Solve above equation for parameter x (IMFP) for the target material
using optical IMFP for Ni (with solver in Excel)
30
30
IMFPs determined from EPI ratios for Au, Ag, Si, and Cu
60 60
50 Ag 50 Au
40 40
IMFP ()
60
30
40 20
20 10
0 0
100 1000 100 1000 31
Electron Energy (eV) Electron Energy (eV)
31
IMFPs determined from EPI ratios for Cr, Fe, Ga, and Graphite
70 60
60 Cr 50 Fe
50 40
40 30
30
20
20
10
10
0 0
100 1000 100 1000
100 100
Ga graphite
80 80
IMFP ()
60 60
40 40
20 20
0 0
100 1000 100 1000 32
Electron Energy (eV) Electron Energy (eV)
32
IMFPs determined from EPI ratios for Mo, Pt, Zn, Ta, and W
5
Mo/Ni 60 50
Elastic peak intensity ratio (Ni-std)
Pt/Ni
4 50 Mo Pt
Ta/Ni 40
W/Ni
40
IMFP ()
Zn/Ni 30
3 30
20
20
2
10 10
0 0
1
100 1000 100 1000
Electron Energy (eV) Electron Energy (eV)
0
100 1000
Electron energy (eV)
80
60 50
70 Zn Ta W
60 50 40
50 40
30
40 30
30 20
20
20
10 10
10
0 0 0
100 1000 100 1000 100 1000
Electron Energy (eV) Electron Energy (eV) Electron Energy (eV)
Solid circles: present work (EPES) , solid lines: optical IMFPs, dotted lines: TPP-
TPP-2M
33
33
Analysis of IMFPs with Fano Plot
- We have analyzed experimentally determined IMFPs using Fano Plots
Plots which
were constructed by plotting values of E/ versus
versus ln E.
E / b a ln( E )
140 140 160
Au Cr
120
100 100 Pt
Ag
Fe Ta
Energy/ (eV/)
80
Energy/ (eV/)
Energy/ (eV/)
60 60 W
Cu 40
Ga Mo
20 20 Zn
0 0
Si 0
graphite
0
0
0 0
0 0
0
0 0
10 4 0
100 1000 100 1000 10 4
100 1000 10 4
Electron energy (eV) Electron energy (eV)
Electron energy (eV)
Sincethedatapointsliesufficientlycloseto
straightlines,FanoplotcanbefitbysimpleBethe
equation.
Thenthevaluesoftheparametersbetaandgamma
werefoundfromalinearleastsquaresanalysis.
34
RMS difference of IMFPs determined by EPES from optical IMFPs (Penn
(Penn
algorithm) and IMFPs from the TPP-
TPP-2M equation
35
35
Summary
We have performed experimental determinations of IMFPs for 13
elemental solids over the 50 eV to 5000 eV energy range from
backscattered elastic-peak intensities using a Ni reference
together with Monte Carlo simulations.
The IMFPs of Ag, Au, Cr, Cu, Fe, Pt, Si, Ta, and W were in
excellent agreement (RMS deviations less than 11%) with those
calculated from the Penn algorithm (optical IMFPs) over the 100
eV to 5000 eV energy range.
36
36
We conclude that the accuracy of IMFPs for elemental
solids calculated from measured energy-loss functions is
about 10 % over the 100 eV to 5000 eV energy range.
37
37
4. IMFP Applications
- Quantitative XPS [1]
38
Effective Attenuation Lengths
The effective attenuation length (EAL) is the parameter to be used in an equation in
place of the IMFP to account for the effects of elastic scattering.
Jablonski and Powell [1] proposed a simple empirical formula for the average EAL
for film-thickness measurements, L, for emission angles between 0 and 50:
L in (1 0 .735 )
in
in tr
where in is the IMFP and tr is the transport mean free path (TMFP) which is derived
from the differential cross section for elastic scattering. This formula was developed
for electron energies between 100 eV and 2 keV,
but should be valid for higher energies.
39
Mean Escape Depths
The mean escape depth (MED) is the average depth normal to the surface from
which the detected electrons escape.
in
in tr
40
Information Depths
The information depth (ID) is the depth normal to the surface from which useful
signal information is obtained.
1
In the absence of elastic scattering, the ID, S, is S in cos ln
where P is a specified percentage of the detected 1 ( P / 100)
signal.
41
Modeling XPS for Thin-Film Structures
The NIST Database for Simulation of Electron Spectra for Surface Analysis (SESSA)
[1,2] provides data for quantitative XPS for X-ray energies up to 20 keV. SESSA can
also perform efficient Monte Carlo simulations of XPS spectra for multi-layered thin-
film samples.
1. http://www.nist.gov/srd/nist100.htm.
2. W. Smekal, W. S. M. Werner, and C. J. Powell, Surf. Interface Anal. 37, 1059 (2005).
42
5. Summary
1. IMFPs have been calculated for 42 elemental
solids, 12 organic compounds, and 21 inorganic 103 42 Elemental Solids
from experimental optical data for electron
43
Optical IMFPs (points) for Li, Be, graphite, diamond, glassy C, and Na
3
10
Na Solid lines show fits
2 with the modified
Inelastic Mean Free Path () 10
Bethe equation
1
Glassy
10 Carbon
Dashed lines show
0 IMFPs from the TPP-
10 Diamond 2M equation
0 Graphite
10
0
Be 3
10 10
Li
0 2
10 10
0 1
10 10
0 0
10 10
1 2 3 4 5
10 10 10 10 10
Electron Energy (eV)
44
Optical IMFPs (points) for Mg, Al, Si, K, Sc, and Ti
3
10
Ti Solid lines show fits
2 with the modified
10
Inelastic Mean Free Path ()
Sc Bethe equation
1
10 K
Dashed lines show
0 IMFPs from the TPP-
10 2M equation
Si
0
10
Al
0 3
10 10
Mg
0 2
10 10
0 1
10 10
0
10
0 10
1 2 3 4 5
10 10 10 10 10
Electron Energy (eV)
45
Optical IMFPs (points) for V, Cr, Fe, Co, Ni, and Cu
3
10
Cu Solid lines show fits
2
10 with the modified
Inelastic Mean Free Path ()
Ni Bethe equation
1
10
Co Dashed lines show
0 IMFPs from the TPP-
10 2M equation
Fe
0
10
Cr
0 3
10 10
V
0 2
10 10
0 1
10 10
0 0
10 10
101 102 103 10 4 105
Electron Energy (eV)
46
Optical IMFPs (points) for Ge, Y, Zr, Nb, Mo, and Ru
3
10
Ru Solid lines show fits
2 with the modified
10
Inelastic Mean Free Path ()
Mo Bethe equation
1
10
Nb Dashed lines show
0 IMFPs from the TPP-
10 2M equation
Zr
0
10
Y
0 3
10 10
Ge
0 2
10 10
0 1
10 10
0 0
10 10
1 2 3 4 5
10 10 10 10 10
Electron Energy (eV)
47
Optical IMFPs (points) for Rh, Pd, Ag, In, Sn, and Cs
4
10
Solid lines show fits
3
Inelastic Mean Free Path () 10 Cs with the modified
Bethe equation
2
10
Sn Dashed lines show
1
10 IMFPs from the TPP-
In 2M equation
0
10
0
Ag
10
Pd
0 3
10 10
0 Rh 2
10 10
0 1
10 10
0 0
10 10
1 2 3 4 5
10 10 10 10 10
Electron Energy (eV)
48
Optical IMFPs (points) for Gd, Tb, Dy, Hf, Ta, and W
3
10
W Solid lines show fits
2 with the modified
10
Inelastic Mean Free Path ()
Ta Bethe equation
1
10
Hf Dashed lines show
0 IMFPs from the TPP-
10 2M equation
Dy
0
10
Tb
0 3
10 10
Gd
0 2
10 10
0 1
10 10
0 0
10 10
101 102 103 104 105
Electron Energy (eV)
49
Optical IMFPs (points) for Re, Os, Ir, Pt, Au, and Bi
3
10
Bi Solid lines show fits
2 with the modified
10
Inelastic Mean Free Path ()
Bethe equation
1
Au
10
Dashed lines show
0
Pt IMFPs from the TPP-
10 2M equation
0
Ir
10
0
Os 3
10 10
0 Re 2
10 10
0 1
10 10
0 0
10 10
101 102 103 104 105
Electron Energy (eV)
50