Inelastic Mean Free Path

The Inelastic Mean Free Path (IMFP): Theory, Experiment, and
Applications
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
I will be talking about Electron scattering in

Surface electron spectroscopy. My talk consists
of 4 part.
The first is introduction.
The second is calculations of IMFPs for wide
variety of materials. I will talk about the
evaluation of energy loss functions, Fano
Plot,.
The third is experimental determinations of
IMFPs with elastic peak electron spectroscopy.
The last is summary.
1
1. Introduction
The electron inelastic mean free path (IMFP) is a basic material

parameter for describing the surface sensitivity of XPS and other
surface electron spectroscopies.
IMFP is needed for quantitative analyses by XPS (matrix
correction), determination of film thicknesses (with effective
attenuation lengths), and estimates of surface sensitivity (mean
escape depths and information depths).
IMFPs have been determined for 75 materials from optical energy-
loss functions with the Penn algorithm for energies from 50 eV to
30,000 eV (previously 50 eV to 2,000 eV)
The TPP-2M formula for predicting IMFPs has been evaluated for
the 50 eV to 30,000 eV range (previously 50 eV to 2,000 eV)
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)
D. R. Penn, Phys. Rev. B 35, 482 (1987). 3
This shows the flow of IMFP calculation from energy

lossfunction.
Electron inelastic mean free path in solid can be
calculated from imaginary part of inverse dielectric
functionorenergylossfunction.
In Penn algorithm, the energy dependence of ELF can be
obtained from experimental optical energy loss function.
As for qdependence, it is very difficult to measure with
experimentalmethod.ThentheLindhardmodeldielectric
functionwasused.Over300eV,weusedthesinglepole
approximationforqdependenceofELF.
3
Conditions and materials for IMFP calculations
- Energy range for IMFP calculation: 50 eV to 30,000 eV

- calculated at equal intervals on a logarithmic energy
scale corresponding to increases of 10 %.
- 42 elemental solids
Li, Be, diamond, graphite, glassy carbon, Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Fe, Co,
Ni, Cu, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Cs, Gd, Tb, Dy, Hf, Ta, W, Re,
Os, Ir, Pt, Au, and Bi
- 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
KK-sum rule (a limiting form of the Kramers-Kronig integral)

E max
Peff (2 / ) E 1 Im[1 / (E )]d (E ) n 2 (0)
0
When E max
: total number of electrons
Z eff Z for material
Peff 1
5
The accuracy of the energy loss function affects the

reliability of IMFPs.
Then it is very important to evaluated energy loss
function with sum rules.
We use two effective sum rules.
Using F-sum rule, we can evaluate the accuracy of
ELF at high energy region.
With KK-sum rule, the accuracy of low energy region
of ELF , especially under 100 eV,
can be evaluated.
When DE max becomes infinity, f-sum value Z eff

equals to the total number of electron for material and
Peff equals to unity if ELF is correct.
5
101
Polyethylene
10-1
Energy loss function and sum-rule
Energy Loss Function

C K-shell
10-3
calculations for organic compounds Valence-
excitations
10-5 band
(e.g., polyethylene) excitations
10-7
10-9 Poly-C2H4
1 10 -11
100 101 102 103 104 105

E(eV)
0.8 20
Polyethylene
Polyethylene f-sum error: 0.0 %
0.6
KK sum
eff
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
This shows the results of sum rule calculations for

polyethylene. This is the energy loss function of
polyethylene. Since polyethylene consists of low
atomic number elements Hydrogen and carbon, its
ELF is very simple.
This peak corresponds to the valence and conduction
electron excitation. This is due to the carbon K-shell
ionization.
This figure shows the F-sum rule results. We see the
contribution of valence electrons ; Nv =12,3 this
value is almost the same as theoretical value.
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
These figures are the calculated results of sum

rule for aluminum and aluminum oxide.
Theoretical values Al = 13 (total electrons )

Al2O3 =50. The error of f-sum rule for Al is -
0.9%, -5.3 % for Al2O3.
-Valence electrons : 3 for Al not clear Al2O3

-K-shell :about 2 for Al:
-For Al2O3 : the shell structure is not clear
compared to Al
7
Sum-rule results for elemental solids and inorganic
compounds
Elements Inorganic compounds
Eelements
40 40
Zr
Error of KK-sun rule (%)

20 20
Error of KK-sum rule (%)
0 0
-20 -20
Nb Sn InSb
InAs
GaAs
-40 -40
-40 -20 0 20 40
-40 -20 0 20 40
Error of F-sum rule (%) Error of F-sum rule (%)
Results for 42 elemental solids Results for 21 inorganic compounds

RMS KK-sum error: 14% (6.7%)
RMS KK-sum error: 9.0 %
RMS f-sum error: 7.6 % RMS f-sum error: 7.4 % 8
These figures show the results of sum rule

calculations for elements and inorganic compounds.
For 42 elemental solids, the root mean square error
of KK-sum rules is 9.0 %. F-sum rule error is 7.8% .
These values indicate these ELF are sufficiently
accurate for IMFP calculations.
As for these compounds ad elements, we plan to

measure optical constants by EELS.
We also plan to calculate optical constants from band
structure calculations. yesterday my colleage
Shinotuka talked abut the calculation of optical
constants for several metals.
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
Average KK-sum error: 2.5 %

(all compounds are within 6% error)
-20
-20 -10 0 10 20
Error of F-sum rule (%)
9
Calculated IMFPs for 42 elemental solids
10 3 42 elemental solids Minima: 10 eV to 150 eV

Inelastic Mean Free Patha ()
IMFP range
- factor of 2.2 at 70eV
- factor of 5.9 at 30,000 eV
10 2
10 1
10 0
10 1 10 2 10 3 10 4 10 5
10
This shows the calculated IMFPs for 42

elemental solids as functions of electron energy
in the 10 eV to 30 000 eV energy range. We
see the minimum values are in the vicinity of 70
eV.
There are large variation at 30 000 eV and very
low energy region. The factor at 30 000 eV is
5.9. This means very large material
dependence.
10
Calculated IMFPs for compounds
21 inorganic compounds
10 3 10 3
12 Organic compounds
Inelastic Mean Free Paths()
Inelastic Mean Free Path()

10 2 100
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)
Minima at 70 eV to 80 eV Minima at 50 eV to 100 eV

IMFP range: < factor of 1.3 (at 70eV, 30 keV) IMFP range: factor > 2.0 (at 70eV, 30 keV)
11
These figures show the calculated IMFPs as

functions of electron energy for 12 organic
compounds and 21 elemental solids.
For organic compounds ,there are minimum values
around 70 - 80 eV. The factor is small, 1.3 at 70 eV
and 30 000 eV.
This is the reason why their variation of valence
electron density are small for organic compounds.
In 21 organic compounds, the minimum points are in
the 50 to 100 eV energy range. In the 70 to 30 000,
the material dependence is almost constant. It is
about 2.0.
11
Modified Bethe equation for IMFP
Bethe equation for total inelastic-scattering cross section in matter

at electron energy E
IMFP equation: Modified Bethe equation for 50 eV to 30,000 eV range
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).
The Bethe.. can be described as this equation.

Mtot2 square of dipole matrix elements for all
possible scattering process.
Based on this equation, we derived this equation for
describing IMFPs in the 50 30,000 eV, We call it
modified Bethe equation for IMFP.
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
In the analysis of energy dependence of IMFPs,

it is convenience to use Fan plots.
Fano plot is expressed as the energy over
lambda versus log E.
Using Modified Bethe equation, Fano plots can

be descried this equation. This has 4
parameters.
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/)
RMS = 0.64% RMS = 0.46%

50 80
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
14
These figures show the Fano Plots for Si and

Ru and results of curve fits with M. Bethe
equation,
The open circles show the calculated IMFPs
from optical data. The solid line is the curve fit
with Modified. Bethe equation. The curve fits
gave excellent results on Si and Ru.
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
E E p2 ln E C E D E 2
15
These are the examples of organic compounds.

Beta-carloten and polyethleye.
The Modified Bethe equation gives also
excellent fits for both compounds over 50 to 30
000 eV energy range.
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
20 RMS = 0.5% RMS = 1.1%

10
0 0
10 1 10 2 10 3 10 4 10 5 10 1 10 2 10 3 10 4 10 5
C D C D
0.0146 0.0815 1.16 31.1 0.0306 0.0469 1.05 53.4
16
These are the examples of inorganic

compounds. Al2O3 and GaAs. For Al2O3, M.
Bethe fit show a good agreement for with
energy range. For GaAs, the agreement is not
good at higher energy region. This compounds
is the worst case in 75 materials in this study.
Fortunately, the difference is not so large,
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
21 inorganic compounds : 0.56 %
Frequency
10
Modified Bethe equation could be used

5
to fit IMFPs over the 50 eV to 30,000 eV
energy range with low RMS deviations
(less than 1.1%)
0
GaAs and Co were the worst case! 0 0.2 0.4 0.6 0.8 1 1.2
RMS deviation (%)
17
I will show the results of modified Bethe

equation fits to calculated IMFPs over the 50 to
30, 000 eV energy range.
This show the histograms of the curve fit results
using % of rms errors. The average of rms
error of elements is 0.5%,
These values are very nice results.
Then, Modified Bethe equation could be used
to fit IMFPs over the 50 to 30,000 eV with low
rms deviations.
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).
Then, We have developed the general formula TPP-

2M empirically from the curve fit results with M.
Bethe equation. Using this equation, we can estimate
the IMFPs in the 50 30000eV at any material.
IMFP can be calculated with these 4 physical
parameters.
From now, we will compare the present calculated

IMFPs with those of TPP-2M equation.
18
Comparison of calculated IMFPs for Si and Ru with TPP-2M
IMFPs
silicon ruthenium
10 3 10 3
Mod. Bethe Eq. Fit

Mod. Bethe Eq. Fit
TPP-2M TPP-2M
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
RMS = 3.0 % ( 50 eV to 30,000 eV) RMS = 5.0 % ( 50 eV to 30,000 eV)
19
These figures shows the comparison of

calculated IMFPs from optical ELF and those of
TPP-2M. This is silicon. This is ruthenium. Red
circles show the calculated IMFPs, Blue solid
line is the results of the curve fit with M. Bethe
equation.
Green doted line show the IMFPs of TPP-2M.
For both elements, the TPP-2M IMFP values

are in good agreement with those of calculated
IMFPs over 50 - 3000 eV energy range,
The rms deviations are 3.0 % and 5 %.
19
Comparison of calculated IMFPs for -carotene and
polyethylene with TPP-2M IMFPs
-carotene Polyethylene

Mod. Bethe Eq. Fit Mod. Bethe Eq. Fit

TPP-2M TPP-2M
100 100
10 10
1
1 10 1 10 2 10 3 10 4
10 1 10 2
10 3
10 4
RMS = 13.1 % (50 eV to 30,000 eV) RMS = 7.9 % (50 eV to 30,000 eV)
20
These are the results of organic compounds.

For beta carotene, TPP-2M shows the lower
IMFP values over 50 - 30 000 eV compared to
optical IMFPs. For polyethlene, the TPP-2M
IMFPs are in good agreement with calculated
IMFPs. Its rms difference is 8%.
20
Comparison of calculated IMFPs for Al2O3 and GaAs with
TPP-2M IMFPs
Al O GaAs
2 3

Mod. Bethe Eq. Fit

Mod. Bethe Eq. Fit
TPP-2M
TPP-2M
100 100
10 10
1 1
10 1 10 2 10 3 10 4 10 1 10 2 10 3 10 4
RMS = 14.5 % (50 eV to 30,000 eV) RMS = 37.3 % (50 eV to 30,000 eV)
21
These are the results of inorganic compounds.

For Al2O3, the IMFP values calculated from
TPP-2M are larger than the optical IMFPs over
50 to 30,000 eV.
On the other hand TPP-2M gives lower values
for GaAs like this. The difference is rather large.
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
RMS difference (%)

RMS difference (%)
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
This shows the RMS differences between

calculated IMFPs and TPP-2M IMFPs for
elemental solids as a function of valence
electron density . The average rms is 13 % for
42 elemental solids over 50 to 30,000 eV
energy range.
This figure show the rms differences as function
of the valence electron density U for element.
Cs, graphite diamond show the large difference.
Except these elements, the rms decrees to
10 %.
This is the results for compounds.

The average rms is 8 % organic compounds
and 14 % for inorganic compounds.
However, Lithium fluoride and gallium arsenide
gave large rms differences. These are mainly 22
Summary of IMFP calculations
We have calculated IMFPs for 50 eV to 30,000 eV electrons in 42

elemental solids, 12 organic compounds, and 21 inorganic
compounds using their energy-loss functions and the Penn
algorithm. The IMFPs were calculated at equal energy intervals on
a logarithmic scale corresponding to increments of 10 %.
These IMFPs could be fitted to the modified Bethe equation for

inelastic scattering of electrons in matter for energies from 50 eV to
30,000 eV. The average RMS deviations in these fits were 0.1 %
(organic) and 0.5 % (elements and inorganic compounds).
23
This RMS values are almost the

same as those found in our fits of
IMFPs calculated previously for the
50 - 2000 eV energy range.
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 %.
S. Tanuma, C. J. Powell, and D. R. Penn, Surf. Interface Anal. 37, 1 (2005).

24
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.
C. J. Powell and A. Jablonski, J. Phys. Chem. Ref. Data 28, 19 (1999).

S. Tanuma, T. Shiratori, T. Kimura, K. Goto, S. Ichimura, and C. J. Powell, Surf. 25
Interface Anal. 37, 833 (2005).
From now, I will talk about the experimental

determination of
It is very important to know.
We have determine
We will compare the resulting experimental

IMFPs with the
25
Elastic-peak electron spectroscopy (EPES)
IMFPs for the Experimental

Electron Energy Configuration
Standard Material
Experimental Ratio of Theoretical Model

Elastic Backscattering for Electron IMFP
Probabilities Transport
Elastic Scattering Material Parameters

Cross Sections (composition, density)
Incident electron beam (E) Elastically scattered electrons (E)
Sample (or reference material)
26
Measurements of
Measurements of EPIs
EPIsby
byabsolute
absoluteCMA
CMA
Measurement of Elastic Peak Intensity 1A

Primary beam: 1
Energy range : 1 eV to 5,000 eV Detector: Faraday cup
(50 eV to 5,000 eV)
Instrument: Absolute Auger Spectrometer
-detection angle (42.3 6) 27
This slide shows the instrument used for the

measurement of elastic peak intensities. This
system was made by Professor Goto. This
system have a CMA and the detector is
Faraday cup to measure the electron current
directly. The measurements of EPIs were done
in 1 to 5000 eV energy range.
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
Elastic peak intensity ratio (Ni-std)

Ag/Ni
Cr/Ni
Pt/Ni
Fe/Ni
Elatic Peak Intensity ratio
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)
low Z: graphite, Si, similar Z: Fe, Cr, Zn, Cu, Ga

medium Z: Ag, Mo high Z: Au, Pt, Ta, W
28
This viewgraph show the measured elastic

peak intensity ratios as functions of electron
energy for 13 elemental solids using Ni
reference.
classify things into three types 4

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
This one show the calculation of , From Monte

Carlo method, we can calculate the peak intensity
from this equation.
The Gt is a instrumental factor; mainly due to the
transmission efficiency of CMA mesh. Fs is surface-
excitation factor.
S means the total path length.
This graph is an example of the histograms of path
length distribution.
In MC calculation, pseudo random number generator

is very important. We use Mersenne twisterm which
was developed by Mtaumoto.
It is proved that the period is 2^19937-1, and the 623-
dimensional equidistribution property is assured
29
Calculation of Elastic -Peak Intensity Ratio to Ni Reference
Elastic-Peak
Determination of IMFPs from EPIs using Ni standard

; remove Gt
f sx / f sNi 1 - Assume initially that surface-excitation effects are negligible
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
: Determination of IMFPs using Ni standard
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
Using path length distributions of Ni-reference

and the target material, the peak intensity ratio
can be described by this equation.
Then, optimizing this condition, we can get
lambda x for target material. This calculations
can be done easily with solver command in
excel.
30
IMFPs determined from EPI ratios for Au, Ag, Si, and Cu
60 60
50 Ag 50 Au
40 40
IMFP ()
Solid circles: present work (EPES)

solid lines: optical IMFPs
30 30 dotted lines: TPP-2M
20 20
10 10
0 0
100 1000 100 1000
60
100
Si 50 Cu
80
40
IMFP ()
60
30
40 20
20 10
0 0
100 1000 100 1000 31
This viewgraph shows the determined IMFPs of

Ag, Au, SI and Cu from their elastic peak in the
50 to 5000 eV,.
The solid circles.
In Au, Ag, Cu, the present IMFPs from EPES
are in excellent agreement with theoretical
values over 200 eV region like this.
However, in Si the EPES-IMFPs coincide well
with optical and TPP-2M IMFPs in the 100 to
1000 eV. Over 1000 and under 100 eV region,
the determined IMFPs are larger than the
theoretical values.
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
32
IMFPs determined from EPI ratios for Mo, Pt, Zn, Ta, and W
5
Mo/Ni 60 50
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
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)
solid symbols :experimentally determined IMFPs

solid lines: fit to the energy/IMFP values with the Bethe equation
equation
E E p2 ln E Simple Bethe equation

34
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
Average RMS (100 eV to 5000 eV):

11.0 % (optical)
10.7 % (TPP-
(TPP-2M)
35
finally I will show you the results of IMFP

comparison.
This is the results of the comparison with
optical IMFPs and, this is the results with TPP-
2M.
The average rms is ..
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.
These IMFPs determined could be fitted with the simple Bethe

formula over the 100 eV to 5000 eV energy range using Fano plots
(average RMS deviation: 9 %)
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]
- Other important parameters [2]:

- Effective attenuation lengths (EALs)
- Mean escape depths (MEDs)
- Information depths (IDs)
- Modeling XPS for Thin-Film Structures [3]
1. C. J. Powell and A. Jablonski, J. Electron Spectrosc. Relat. Phenom. (in press).

2. C. J. Powell and A. Jablonski, Nucl. Instr. Methods Phys. Res. A 601, 54 (2009).
3. W. S. M. Werner, W. Smekal, and C. J. Powell, Surf. Interface Anal. 37, 1059 (2005).
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.
The plot shows as a function of electron

energy for six illustrative elemental solids [2].
1. A. Jablonski and C. J. Powell, J. Vac. Sci. Technol. A 27, 253 (2009).

2. C. J. Powell and A. Jablonski, J. Electron Spectrosc. Relat. Phenom. (in press).
39
Mean Escape Depths
The mean escape depth (MED) is the average depth normal to the surface from
which the detected electrons escape.
In the absence of elastic scattering, the MED, D, is D in cos where is the

electron emission angle (with respect to the surface normal).
When elastic scattering is considered, an empirical formula for D proposed by

Jablonski and Powell [1] can be used for emission angles between 0 and 50:
D in cos (1 0.736 )
This formula was developed for electron energies between 100 eV and 2 keV,
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.
When elastic scattering is considered, an empirical formula for S proposed by

Jablonski and Powell [1] can be used for emission angles between 0 and 50:
1
S in cos (1 0.787 ) ln
1 ( P / 100)
This formula was developed for electron energies between 100 eV and 2 keV,
in

in tr
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.
Version 1.2 of SESSA (expected to be

released in fall, 2009) will include the
capability to perform XPS simulations
with varying amounts of X-ray
polarization (both linear and circular).
This capability will make SESSA
useful for XPS applications with
synchrotron radiation.
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
Inelastic Mean Free Path ()

energies from 50 eV to 30 keV.
2. The modified Bethe equation fits the optical 10
2
IMFPs well over the entire energy range.

3. The TPP-2M equation provides reasonable
estimates of IMFPs over the entire energy 10
1
range (although there were large deviations

for graphite, diamond, Cs, GaAs, and LiF).
4. IMFPs from elastic-peak electron spectroscopy 100
1 2 3 4
10 10 10 10
experiments generally agree well with the Electron Energy (eV)
optical IMFPs.
5. Simple analytical formulae have been developed to provide useful estimates of
effective attenuation lengths (for film-thickness measurements), mean escape
depths, and information depths (for estimates of surface sensitivity). These
formulae enable convenient corrections for elastic-scattering effects (for 50).
6. The NIST SESSA database provides physical data (including IMFPs from the
TPP-2M equation) for energies up to 20 keV. A planned enhancement will enable
simulations of XPS spectra with polarized X-rays.
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
44
Optical IMFPs (points) for Mg, Al, Si, K, Sc, and Ti
3
10
Ti Solid lines show fits
2 with the modified
10
Sc Bethe equation
1
10 K
Dashed lines show
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
45
Optical IMFPs (points) for V, Cr, Fe, Co, Ni, and Cu
3
10
Cu Solid lines show fits
2
10 with the modified
Ni Bethe equation
1
10
Co Dashed lines show
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
46
Optical IMFPs (points) for Ge, Y, Zr, Nb, Mo, and Ru
3
10
Ru Solid lines show fits
2 with the modified
10
Mo Bethe equation
1
10
Nb Dashed lines show
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
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
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
48
Optical IMFPs (points) for Gd, Tb, Dy, Hf, Ta, and W
3
10
W Solid lines show fits
2 with the modified
10
Ta Bethe equation
1
10
Hf Dashed lines show
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
49
Optical IMFPs (points) for Re, Os, Ir, Pt, Au, and Bi
3
10
Bi Solid lines show fits
2 with the modified
10
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
50

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The Inelastic Mean Free Path (IMFP): Theory, Experiment, and

I will be talking about Electron scattering in

The electron inelastic mean free path (IMFP) is a basic material

D. R. Penn, Phys. Rev. B 35, 482 (1987). 3

This shows the flow of IMFP calculation from energy

- Energy range for IMFP calculation: 50 eV to 30,000 eV

KK-sum rule (a limiting form of the Kramers-Kronig integral)

The accuracy of the energy loss function affects the

When DE max becomes infinity, f-sum value Z eff

Energy Loss Function

100 101 102 103 104 105

This shows the results of sum rule calculations for

These figures are the calculated results of sum

Theoretical values Al = 13 (total electrons )

-Valence electrons : 3 for Al not clear Al2O3

Error of KK-sun rule (%)

Error of F-sum rule (%) Error of F-sum rule (%)

Results for 42 elemental solids Results for 21 inorganic compounds

These figures show the results of sum rule

As for these compounds ad elements, we plan to

Average KK-sum error: 2.5 %

10 3 42 elemental solids Minima: 10 eV to 150 eV

This shows the calculated IMFPs for 42

Inelastic Mean Free Path()

Minima at 70 eV to 80 eV Minima at 50 eV to 100 eV

These figures show the calculated IMFPs as

Bethe equation for total inelastic-scattering cross section in matter

IMFP equation: Modified Bethe equation for 50 eV to 30,000 eV range

The Bethe.. can be described as this equation.

In the analysis of energy dependence of IMFPs,

Using Modified Bethe equation, Fano plots can

RMS = 0.64% RMS = 0.46%

These figures show the Fano Plots for Si and

These are the examples of organic compounds.

20 RMS = 0.5% RMS = 1.1%

These are the examples of inorganic

21 inorganic compounds : 0.56 %

Modified Bethe equation could be used

I will show the results of modified Bethe

Then, We have developed the general formula TPP-

From now, we will compare the present calculated

Inelastic Mean Free Path()

RMS = 3.0 % ( 50 eV to 30,000 eV) RMS = 5.0 % ( 50 eV to 30,000 eV)

These figures shows the comparison of

For both elements, the TPP-2M IMFP values

calculated IMFPs calculated IMFPs

Inelastic Mean Free Path()

Mod. Bethe Eq. Fit Mod. Bethe Eq. Fit

These are the results of organic compounds.

calculated IMFPs calculated IMFPs

Inelastic Mean Free Path()

These are the results of inorganic compounds.

RMS difference (%)

This shows the RMS differences between

This is the results for compounds.

We have calculated IMFPs for 50 eV to 30,000 eV electrons in 42

These IMFPs could be fitted to the modified Bethe equation for

This RMS values are almost the

S. Tanuma, C. J. Powell, and D. R. Penn, Surf. Interface Anal. 37, 1 (2005).

C. J. Powell and A. Jablonski, J. Phys. Chem. Ref. Data 28, 19 (1999).

From now, I will talk about the experimental

We will compare the resulting experimental

IMFPs for the Experimental

Experimental Ratio of Theoretical Model