XPS Atomic Concentration Calculation

Advanced Processing
Quantification
Peak Area definition is important to ensure reliable quantification.
Uncertainties in peak area have a direct influence on the accuracy of any
quantification data.
When data is quantified, the peak areas are measured, suitable sensitivity factors
are applied
pp to the data and corrections for the instrument transmission function
and energy compensation factor (ECF) are made.
The standard quantification library data provide a good first approximation
quantification
qua t cat o but in so
somee cases more
o e accu
accurate
ate results
esu ts may
ay be obta
obtained
ed with
t tthe
e
use of standards, relevant to the particular analysis being performed.
It is assumed that the depth distribution of all the elements is homogenous. This is
often not true (e.g. an overlayer of carbon is often present) but this method
provides a simple and consistent first approximation.
Quantification of XPS data is a complex subject and to calculate the composition in
more detail typically requires a number of assumptions to be made about the
sample; effectively you need to know what the sample is before you quantify and
this is where standards have an important function
20
Quantification
The intensity of a peak is related in some way to the number of atoms that generate
that peak
g IA  NA
e.g.
Where IA is the intensity of a peak and NA is the number of atoms of element A
Each transition (e.g.

(e g C1s,
C1s Al2p,
Al2p Si2s) has it’s
it s own ‘probability’
probability of occurring - referred
to a ‘sensitivity factor’ and are obtained from libraries.
These are generally referred to the Scofield or Wagner libraries
e.g. IA = NF.NA (NA = IA /NF)
where NF is some kind of normalisation factor, which includes terms for the
efficiency (transmission) of the analyser at different kinetic energies, electron
mean free
f path
th () and
d th
the ‘Sensitivity’
‘S iti it ’ ffactor
t
21
Quantification
Although
Alth h people
l use th
the numbers
b th
there are severall sources off uncertainty
t i t iin th
the
result - These can be due to:
• Determination of the peak intensity?

How do you measure a peak area, where do you start from and to, what do you
include, what shape background etc
• Accuracy of Sensitivity Peak Libraries?

Different libraries give different results - which is right?
• Accuracy of the Transmission Function?

How well defined is the function for a particular instrument
• Other Factors include determination of , structure of the surface (layers, islands

etc)
XPS is good for quantification on a relative scale - comparing similar samples,

consistent
i t t measurementt and dddata
t treatment
t t t and
d looking
l ki ffor trends
t d
But absolute numbers have a great deal of uncertainty due to above
22
Quantification
Name Start Peak End Area (P) Area (N) Atomic Peak Q SF TXFN Backgnd
BE BE BE CPS.eV % Type (Scofield)
B1s 196.0 189.1 180.2 40456.07 2.3977 45.4 Standard 1 0.376 592.41 Smart
C1s 298 0
298.0 283 3
283.3 279 2
279.2 24177 75
24177.75 0 5504
0.5504 10 4
10.4 Standard 1 1 000
1.000 615 35
615.35 Smart
N1s 410.0 396.7 392.2 132468.29 1.8498 35.0 Standard 1 1.676 645.68 Smart
O1s 545.0 531.0 525.2 57212.46 0.4833 9.2 Standard 1 2.881 686.19 Smart
Typical Spectra defined

Peak Area calculated by software after removal of
background (Smart)
Effect of peak definition?
How is Area (N) calculated?
23
Quantification – Peak Definition
C1s 298 0
298.0 283 3
283.3 279 2
279.2 24177 75
24177.75 0 5504
0.5504 10 4
10.4 Standard 1 1 000
1.000 615 35
615.35 Smart
N1s 1 410.0 396.7 392.2 132468.29 1.8498 35.0 Standard 1 1.676 645.68 Smart
C1s 298.0 283.3 279.2 24177.75 0.5504 10.6 Standard 1 1.000 615.35 Smart
Small changes in
peak definition
can effect
quantification
24
Quantification – Area Normalization - Transmission Function
C1s 298 0
298.0 283 3
283.3 279 2
279.2 24177 75
24177.75 0 5504
0.5504 10 4
10.4 Standard 1 1 000
1.000 615 35
615.35 Smart
P kA
Peak Area N
Normalization
li ti
The Peak Area is corrected for the total dwell time per channel, number of scans
and energy channel width
width.
Normalised Peak Area = Peak Area / (SF * TXFN * ECF)

SF = sensitivity factor
TXFN = transmission function
ECF = energy compensation factor
25
Quantification – Sensitivity Factors
C1s 298 0
298.0 283 3
283.3 279 2
279.2 24177 75
24177.75 0 5504
0.5504 10 4
10.4 Standard 1 1 000
1.000 615 35
615.35 Smart
Quantification
Q tifi ti Lib
Libraries
i
A number of libraries are supplied as standard
with the Avantage data system. These are
derived from sensitivity factors generated by
Wagner and Scofield.
The Scofield sensitivity factors are theoretically
derived from the photo-ionisation probabilities
The Wagner values were determined
empirically from a large number of compounds
in the early 1980s
1980s. The actual libraries have
been optimised for the appropriate X-ray
anode, e.g. MGWAGNER, ALSCOF etc.
26
Quantification – Sensitivity Factors
C1s 298 0
298.0 283 3
283.3 279 2
279.2 24177 75
24177.75 0 5504
0.5504 10 4
10.4 Standard 1 1 000
1.000 615 35
615.35 Smart
Two libraries are used but they have to be used in slightly different ways
Scofield - A theoretical sensitivity factor data base, based on C1s = 1
(i.e. A calculation which gives a number relating to the number of photoelectrons generated
byy a number of photons
p hitting
g the sample)
p )
For this we need to add in a term to account for the depth of analysis (i.e.  and is generally
KE0.6 or using the TPP-2M method)
Wagner - An empirical sensitivity factor data base, based on F1s = 1
(i e Real measurements done on an instrument on a large number of known compounds
(i.e.
and working out relative sensitivity factors).
For this we need to add in a term to correct for the fact this was generated on a different
type of analyser (A CMA rather than our HSA). This is done by multiplying by the KE of the
peak used.
used
(The term  is already included in the analysis)
Both libraries can be used - but different results on the same set of data may be obtained!!
27
Quantification – ECF - energy compensation factor
Name Peak Area (P) Area (N) Atomic
BE CPS.eV %
B1s 189.1 40456.07 2.3977 45.4
C1s 283 3
283.3 24177 75
24177.75 0 5504
0.5504 10 4
10.4
N1s 1 396.7 132468.29 1.8498 35.0
O1s 531.0 57212.46 0.4833 9.2
The energy compensation factor is applied depending on library being used.

The Wagner factors have assumed an instrument transmission function of KE-1. The
inelastic mean free path (IMFP) term is effectively included within the sensitivity factor.
For Scofield a choice of a simple KEn where generally n=0

n=0.6,
6 or the TPP
TPP-2M
2M method –
is required.
In the Peak Table the Area (N) indicates which method has been used
The selection is set in the Peak Table Property page.
28
Quantification – TPP-2M energy compensation factor
Name Peak Area (P) Area (N) Atomic
BE CPS.eV %
B1s 189.1 40456.07 2.3977 45.4
C1s 283 3
283.3 24177 75
24177.75 0 5504
0.5504 10 4
10.4
N1s 1 396.7 132468.29 1.8498 35.0
O1s 531.0 57212.46 0.4833 9.2
Whatt is
Wh i TPP-2M?
TPP 2M?
An alternative to using the KE0.6 value is to use an average value as derived
from the Tanuma, Powell, Penn 2 Method (TPP-2M) [S.Tanuma, C.J.Powell
and D
D.R.Penn
R Penn - Surface and Interface Analysis,
Analysis Vol 21 , 165
165-176
176 (1993)]
(1993)].
This is a more detailed approach to calculating Inelastic Mean Free Paths

(IMFP)
29
The full
f expression contains several terms associated with the physical
properties of the surface – many of which cannot be determined by XPS
analysis.
The above expression can be simplified to a more general approach using

average matrix values: (Briggs & Grant, p363, eqns 53-55) and assuming Eg = 0
4 684  = 6.767
Where NV = 4.684, 6 767 and M = 137
137.51
51
30
3.5 Comparison of KE0.6 and TPP-
2M methods
3
Note slight difference in
2.5 compensation at different
ath (nm)
kinetic energies
n Mean Free Pa
2
This would lead to slight
1.5 TPP differences in quantification
KE Pow numbers
b
Electron
1
Thus care required that a
0.5
consistent approach is used
for any quantification
0
0 200 400 600 800 1000 1200 1400 ii.e.
e Scofield and TPP-2m
Kinetic Energy (recommended)
Or
Scofield and KE0.6
31
Quantification – Summary
Name Peak BE Area (N) TPP‐2M Atomic % Comparison of KE0.6 and TPP-2M
B1s 189.1 2.3977 46.2 methods using the same data
C1s 283 3
283.3 0 5504
0.5504 10 6
10.6
Thus care required that a consistent
N1s 396.7 1.7597 33.9
approach is used for any
O1s 531.0 0.4833 9.3 quantification including
Name Peak BE Area (N) KE0.6 Atomic % survey/narrow scan, peak definition
B1s 189.1 2.4590 46.9 and choice of library
C1ss
C 283.3
83 3 0.5573
0 55 3 10.6
06
ii.e. S
Scofield
fi ld and
d TPP
TPP-2M
2M
N1s 396.7 1.7524 33.4 (recommended)
O1s 531.0 0.4714 9.0 Or
Scofield and KE0.6
06
Narrow TPP-2M
(full N range) Narrow TPP-2M Narrow KE0.6 Survey TPP-2M
B1s 45.4 46.2 46.9 45.4

C1s 10.4 10.6 10.6 10.7
N1s 35.0 33.9 33.4 34.7
O1s 9.2 9.3 9.0 9.2
32

XPS Atomic Concentration Calculation

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XPS Atomic Concentration Calculation

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Advanced Processing

Each transition (e.g.

These are generally referred to the Scofield or Wagner libraries

e.g. IA = NF.NA (NA = IA /NF)

• Determination of the peak intensity?

• Accuracy of Sensitivity Peak Libraries?

• Accuracy of the Transmission Function?

• Other Factors include determination of , structure of the surface (layers, islands

XPS is good for quantification on a relative scale - comparing similar samples,

Typical Spectra defined

Normalised Peak Area = Peak Area / (SF * TXFN * ECF)

The energy compensation factor is applied depending on library being used.

For Scofield a choice of a simple KEn where generally n=0

The selection is set in the Peak Table Property page.

This is a more detailed approach to calculating Inelastic Mean Free Paths

The above expression can be simplified to a more general approach using

B1s 45.4 46.2 46.9 45.4

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