Fresenius' Journal of

Fresenius J Anal Chem (99) 341:116-120

Springer-Verlag 1991
Deconvolution of XPS spectra
D. Sprenger 1 and O. Anderson 2
1 Institut ffir Anorganisehe und Analytische Chemic, Universitfit Mainz, W-6500 Mainz, Federal Republic of Germany
2 SCHOTT Glaswerke, Postfach 2480, W-6500 Mainz, Federal Republic of Germany
Received February 25, 1991
Summary. The resolution of XPS spectra is limited mainly
by instrumental parameters like the spectral line width of
the exciting X-ray source and the finite energy resolution
of the electron analyzer. If the line broadening functions
resulting from the instrumental setup can be estimated and
expressed by a spectrometer function, a mathematical re-
calculation of the intrinsic signal is possible by deconvolu-
tion. With the method presented in this paper, a resolution
enhancement by a factor of 3 can be obtained. Measured
spectra of physically correlated spin orbit doublets have been
deconvoluted, and it is shown, that the intensity ratios and
the positions are comparable with results obtained by highly
resolved measurements using monochromatized X-rays and
long acquisition times. Informations on phase compositions
by an interpretation of chemical shifts of less then 0.6 eV are
possible, too.
Introduction
XPS is an useful analytical tool for the investigation of solid
surface layers to yield qualitative and quantitative informa-
tion about the composition of the sample [1, 2]. By
recording highly resolved spectra small differences in the
binding energy of elements due to different chemical en-
vironments (chemical shifts), may be detected and therefore
a determination of the phase composition may be possible
[31.
Whereas the intensity of an observed signal is pre-
dominantly determined by the sample, the linewidth is
strongly influenced by apparative parameters. In particular,
in the case of composite spectra resulting from small
chemical shifts, the energy resolution can be insufficient. An
improvement of the energy resolution can be obtained by
the use of an X-ray monochromator, which results in a
reduction of the X-ray line width from 0.85 eV to less than
0.4 eV for A1 K~ excitation [4]. Unfortunately, the acquisition
time strongly increases in this case. Another possibility is
given by a mathematical treatment of the measured spectra.
The lineshape g(x) of an observed XPS signal can be de-
Offprint requests to: D. Sprenger
scribed by a convolution of the intrinsic signal f(x) of the
photoemission process with a spectrometer function h(x),
+oo
t ~
g(x) = } f(x - t) h(t) dt -= f(x) h(x), (1)
- oo
with
h(x) = EQ(x) EX(x) EA(x),
which includes all line broadening contributions of the in-
strumental setup. These line broadening functions are the
analyser resolution function EA(x), the Gaussian distribu-
tion EQ(x) caused by the charging effects on insulators, and
the line shape of the exciting photons of the X-ray source
EX(x). If the spectrometer function h(x) is known accurately,
it should be possible to recalculate the intrinsic signal f(x)
by inversion of Eq. (1). This procedure is called ' deconvolu-
tion'. In practice, the solution of the inversion of the integral
Eq. (1) is not unique because any function F(x) which
satisfies Eq. (2), may be added to a solution f(x) and results
in another solution:
+oo
f F( x- t ) h(t) = (2)
dt 0.
- c o
This is given, for example, for a noise function consisting
of rapid fluctuations around their zero intensity. Before a
successful deconvolution can be applied, the noise has to
be reduced by smoothing or low-pass filtering, and the
spectrometer function has to be determined with sufficient
accuracy.
Smoothi ng
Smoothing is a process that attempts to increase the correla-
tion between the measured points while supressing the
uncorrelated noise. This operation has to be carried out in
a most effective and least distorting way. For performing a
deconvolution, the usually performed smoothing by spline
and polynomial algorithms is insufficient. Good results were
obtained by a least squares approach [5] and by optimal
filtering based on Fourier transform methods [6]. To avoid
noise and spurious oscillations to be transferred into the
0
C)
100000
80000
60000
40000
20000
0
Au 4 f
, MgKa t
92 8;2 72
Binding energy [ e V ]
Fig. 1. Fitted XPS spectrum of the Au 4f signal of an evaporated
gold sample excited with Mg K~, after background subtraction
deconvoluted spectrum, as it is often seen in the literature,
the initial data should have a good signal-to-noise ratio. A
correct digital filtering is an indispensable requirement to
obtain good deconvolution results.
Determination of the spectrometer function
The spectrometer function h(x) includes the line broadening
functions of the electron analyser and the contributions
caused by the exciting X-ray source, and results in a convolu-
tion with each other.
a) The analyser function
The resolution and intensity behaviour of the electron ana-
lyser is determined by geometric parameters like the width
of the entrance and exit slits and by the selected pass energy.
If the analyser is used in the constant pass energy mode, the
transmission energy (pass energy) and the absolute energy
resolution remain constant in the whole energy area. A theo-
retical calculation of the analyser function [7] does not
produce satisfying results for a successful deconvolution.
Therefore an experimental determination is necessary. If an
UV-source is used, an accurate determination of the analyser
function in dependence on the pass energy is possible [8].
These analyser function consists of a Gaussian line shape
at lower pass energy, which becomes more triangular with
increasing pass energy. These results are in agreement with
theoretical calculations [7].
b) Energy distribution of the exciting X-rays
The X-ray lines mainly used in XPS investigations are A1
K~ and Mg K~ with characteristic energies of 1486.6 and
1253.6 eV and a theoretical FWHM of 0.85 and 0.70 eV,
respectively. The Lorentzian shape of the X-ray emission
lines and their intensity ratios are well known [9], and the
energy distribution of the X-rays can be calculated. In
practice, the exact distribution depends on the oxidation
state of the anode, which results mainly in changed energy
and intensity ratios of the satellites [9, 10]. An exact determi-
nation of the energy distribution of the X-ray source required
117
1.0
0 . 6 -
o . 4 -
O. 2 -
a
o.o-
i : 1 /
0.0 _ b
0. 4-
o. 2-
0.0
10
a Binding energy [eV]
==
2
ro
4J~ - 0 . 4
- 0 . 8
4 ~ - 1 . 2
H
- 1 . 6
- 2 . 0
0 , 8 -
Fig. 2. Simulated spectrum b consisting of 3 Gaussian lines with a
FWHM of 0.2 eV, its convolution with a Gaussian response func-
tion with a width of 1.0 eV a, the 2-nd derivative spectrum c of
the convoluted spectrum a, and the deconvoluted spectrum after
50 iterations d
for deconvolution applications is always affected by the
energy distribution of the analyser function. Therefore, the
Au 4f lines of a clean gold sample (Au sputtered onto Ta)
was measured over an energy region of 20 eV and, after
background subtraction [11], fitted with a symmetric Voigt
profile (Fig. 1). Small asymmetries resulting from valence
band interaction, could be neglected [12]. The summation of
the Au 4f 7/2 subspectra and the corresponding satellites
(Fig. 1) results after deconvolution with the intrinsic
lineshape of the Au 4f state (FWHM = 0.25 eV [13]) in the
spectrometer function, which is valid for all spectra mea-
sured under the same apparative conditions. This response
function can be used for deconvolution and should be
verified after some time to take changes of the anode surface
into account.
Deconvolution
Several deconvolution procedures to solve Eq. (2) (for a
review see [14]) have been used in the literature. All these
methods are based on the convolution theorem, which states
that the convolution of two functions could be expressed by
the product of the Fourier transform of these functions.
Most of them are strongly influenced by the overall presence
of noise or produce artifacts in the deconvoluted spectrum
like nonphysical satellites which are related to the Gibbs
phenomenon. Useful results can be obtained by an applica-
118
c
r -
J
1 .4 15.6
X Ar 3p
5'.8 ' ' I 1 6 . 0 1 6 . 2
Binding energy [eV]
Fig. 3. UPS spectrum of the Ar 3p signal excited with HeI after
background subtraction a, after smoothing b, after several steps of
deconvolution c, d, and a measured spectrum with a comparable
energy resolution
f--
f8
4J
43
H
' 1. 0
0 . 8
0 . 6
0. 4
0. 2.
0. 0
0. 2
0. 0
i ] 0
S 2p
k
160. 0 t 6 2 . 0 t 6 4 . 0 1 6 6 . 0 1 6 8 . 0
Bi nd&ng En e r g y (eV)
Fig. 4. XPS spectrum of the S 2p signal of a sulphur sample excited
with Mg K, after background subtraction a, after smoothing b, and
after deconvolution c
tion of the iterative "poi nt simultaneous over-relaxated
Jansson al gori t hm" [15, 16]:
f,(x) = f , - l(X) + a, (y) [g(x) - f , _ t(x) (9 h(x)]. (3)
The essence of this met hod lies in a successive refinement of
an appr oxi mat e solution fn(x) of the intrinsic signal fix). The
so-called rel axat i on function an(y) influences the conver-
gence of the algorithm, but also affects the relative intensities
and the peak shapes in the deconvol ut ed spectrum. For XPS
spectra with intrinsic Lorent zi an shapes, the function
an(y) = amax(Y 2 4- y)/2 with y(x) = If, - l(x)l (4)
produces good results. Too high values for area x makes the
met hod divergent, so the most suitable values of amax depend
on the data. I n practice, we st art with a value for the par ame-
ter amax of 1.0 increasing by 0.1 in each iteration, to make the
convergence as rapi d as possible. The number of iterations
depends on the number and distances of the overl appi ng
lines and on the accuracy of the response function, but does
not exceed 50 iterations. I f the initial dat a have a good signal-
to-noise ratio, a resolution enhancement of mor e t han a
fact or of 3 can be obtained. Wi t h our pr ogr am written in
MS-QuickBasic and Assembl er the deconvol ut i on of one
spect rum needs less t han 5 mi n on an I BM- AT [17].
Results from deconvolution studies
For an initial demonst rat i on of the met hod several syn-
thetically and measured spectra of physically correlated spin
orbi t doublets were deconvoluted.
A synthetical spect rum consisting of 3 Gaussi an peaks
with a FWHM of 0.2 eV (Fig. 2b) was convol ut ed with a
Gaussi an response function of 1.0 eV FWHM. The positions
of the mi ni mum negative intensities in the second derivative
(Fig. 2c) of the convol ut ed spect rum (Fig. I a) represent the
peak positions in the pr i mar y spect rum (Fig. 2 b). Aft er 50
iterations, the peak positions and the relative intensities of
the final results (Fig. 2d) are identical to the initial spectrum,
only the linewidths show some remai ni ng broadeni ng.
The spin-orbit doubl et of the Ar 3 p level excited with He I
was measured with a pass energy of 20 eV correspondi ng to
an energy resolution of 230 mV (Fig. 3a). Aft er de-
convol ut i on with the analyser function, the spect rum results
in a line of 75 meV FWHM (Fig. 3 d). This result is compar -
able to a measured spect rum with a pass energy of 5 eV and
a correspondi ng linewidth of 70 meV FWHM (Fig. 3 e) [8].
Furt her tests are concerned with the deconvol ut i on of
signals collected f r om solids excited with Mg K~ radi at i on
and measured with a pass energy of 20 eV and a slit width
of 3 x 10 mm. For this, elemental sulfur and KBr were pre-
pared in small discs. The measured S 2p signal of the sulfur
sampl e aft er backgr ound subt ract i on is shown in Fig. 4a.
After smoot hi ng and deconvol ut i on the spect rum results in
a line for the S 2pa/2 signal with a FWHM of 0.52 eV
(Fig. 4c) and a spin-orbit separat i on of 1.25 eV. Only small
differences between the fitted t heory and the deconvol ut ed
spect rum occur f r om a surface cont ami nat i on and the statis-
tics of the measured spectrum.
The measured Br 3d signal of the KBr sampl e (Fig. 5 a)
shows a st rong asymmet ri c line resulting f r om the spin-orbit
splitting. Aft er smoot hi ng and 20 iterations the spect rum
results in two well separat ed lines with a FWHM of 0.71 eV
for the Br 3d5/2 signal, and a spin-orbit separat i on of l . 01 eV
(Fig. 5c).
The Si 2p spect rum recorded f r om a mechanically
cleaned silicon wafer aft er backgr ound subtraction, is shown
in Fig. 6 a. A small signal appeari ng at higher energy, repre-
sents an oxidic coverage. No spin-orbit doubl et is visible
in the measured spect rum, onl y a weak asymmet r y can be
observed. The deconvol ut i on [18] results in two wel l
separat ed signals (Fig. 6d) with a distance of 0.62 eV and an
119
2
==
4~
C
~. 0
0. B
0. B
0, 4
0. 2
0. 0
0. 2
0. 0
0. 2
0. 0
/ -,~, Br 5d
/
__ b
C
Table 1. Parameters and binding energies (BE) from a silicon wafer,
a sulfur- and a KBr disc after deconvolution
Sample Signal BE FWHM Relative
(eV) (eV) intensity (%)
Sulfur S 2p3/2 163.81 0.52 66.30
S 2px/z 165,06 0.64 33.70
KBr Br 3d5/2 68.43 0.71 60.04
Br 3d3/2 69.44 0.81 39.96
Silicon wafer Si 2p3/ 2 99,54 0,52 65.82
Si 2p~/2 100.16 0.56 34.18
~1
0.8 t
Au 4f
65. 0 67. 0 69. 0 7t . 0 73. 0
Bi ndi ng Ener' gy (eV)
Fig. 5. XPS spectrum of the Br 3d signal of a KBr sample excited
with Mg K, after background subtraction a, after smoothing b, and
after deconvolution e
1.0-
0.8-
0.6~
0.4
0.2-
0.0~,
0.2
H 0.0
0"2 I
0.0
0"2 I
0.0
97.0 99.0 t0:t .0 ~03. 0 J,05.0
Bi ndi ng Ener' gy (eV)
Fig. 6. XPS spectrum of the Si 2p signal of a silicon wafer excited
with Mg K, after background subtraction a, after smoothing b,
intermediate result c and final result d of the deconvolution
area ratio of 2: ~l, whi ch agree welt with results recorded on
a Si(111) crystal face with a high resol uti on ESCA instru-
ment [19].
The experi mental values of the measured sulfur and KBr
" sampl es and the silicon wafer are summari zed in Table 1.
In addition to the limited resol uti on by use of a non-
c
x~
[_
m
c
m
4J
c
H
b
- i!Dj :
ok. : : . ]
20 zxBi ndi ng Energy (eV)
Fig. 7. XPS spectrum of the Au 4f signal of an evaporated gold
sample excited with Mg K, with the calculated background a, after
smoothing b, after deconvolution of the contributions of the X-ray
source c and after an additional deconvolution o the anatyser
function d
monochromat i zed X-ray source, the measured spectra are
distorted also by the appearence of X-ray satellites, whi ch
can be removed by a deconvol uti on wi th a response function
including the characteristic distribution of the X-ray source.
Fig. 7 a shows the recorded Au 4f signal. After background
subtraction and smoot hi ng (Fig. 7b), first the distribution
of the X-ray source is deconvol uted (Fig. 7 c), and finally the
distribution of the analyser (Fig. 7d). This deconvol uti on
results in two lines wi th a FWHM of 0.3 eV, whi ch is close to
the assumed intrinsic line width of 0.25 eV [13]. In practice, it
is much better to deconvol ute the spectrum in a single step
wi th a response functi on including the analyser function as
well as the distribution of the X-ray source.
A typical appl i cati on of the deconvol ut i on is given in
the interpretation of signals from insulators. Because of the
120
1. 0
~ 0. 8
0. 6
0.4
0. 2,
H
0. 0
0. 2
0. 0
0. 2
0. 0
/ / ' / "~"- - A1203_Si02
/ \ cerami cs
/
/"
528, 0 530. 0 532, 0 534. 0 536, 0 538. 0
Bi ndi ng Ener gy (eV)
Fig. 8. XPS Ols spectrum of an A1203 SiOz ceramics after back-
ground subtraction a, after smoothing b and the fitted result after
deconvolution c
Table2. Parameters and binding energies (BE) from the
Al/O3 SiO2 sample after deconvolution
Oxygen bond BE FWHM Relative
(eV) (eV) intensity (%)
=A1- O- AI = 531.6 1.17 24.13
- Si - O- Si - = 532.3 1.00 35.06
- Si - O- H 532.9 1.01 30.08
=A1- O- H 533.4 1.14 10.72
shifts, quantitative determinations of relative compositions
wi t hout use of sensitivity factors are possible. The re-
quirements are a well known spectrometer function, a good
statistics of the initial data, and a correct application of
digital smoot hi ng filters. Wi t h the procedure described, it is
possible to use the deconvolution as a st andard procedure
in the evaluation of XPS-spectra.
Acknowledgements. The authors are grateful to H. Bach (Schott
Glaswerke) and W. Meisel (University of Mainz, FRG) for
enlightening discussions. One of the authors (D.S.) gratefully
acknowledges the financial support granted by the "Schott
Glaswerke Fonds zur F6rderung des wissenschaftlichen Nach-
wuchses."
surface charging, the signals are broadened and an interpre-
tation in terms of elemental signals correspondi ng to dif-
ferent chemical states is not possible. In Fig. 8a, the O Is
signal of a sintered A1203 SiO2 ceramics is shown [19].
After background subtraction and smoothing, a slight fine
structure can be observed (Fig. 8b). The deconvolution
taking into account t hat the response function is broadened
by a Gaussian charging distribution [19], results in four
well separated peaks (Fig. 8 c). The mol ar composi t i on A1: Si
44: 56 as calculated from the intensity ratios obtained by a
least squares fit, is close to the theoretical composi t i on of
41 : 59. The absolute binding energies calibrated by use of a
gold dot, are in good agreement with the published dat a of
531.6 eV and 533.3 eV for oxygen in A1203 and AI(OH)3,
respectively [20]. The fitting results are summarized in
Table 2.
Conclusion
It is demonst rat ed that by correct application the Jansson
algorithm can be used for routine investigations without
produci ng artifacts and additional noise. In dependence on
the signal-to-noise ratio of the initial data, a resolution en-
hancement of at least a fact or of 2- 3 is possible. The
algorithm can also be used for the elimination of the satellites
occurring from a non-monochromat i zed X-ray source. In
connection with an accurate determination of chemical
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