Applied Surface Science 387 (2016) 155–162

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Uniqueness plots: A simple graphical tool for identifying poor peak

fits in X-ray photoelectron spectroscopy
Bhupinder Singh a , Anubhav Diwan a , Varun Jain a , Alberto Herrera-Gomez b , Jeff Terry c ,
Matthew R. Linford a,∗
a
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, 84606, USA
b
CINVESTAV-Unidad Queretaro, Queretaro, 76230, Mexico
c
Department of Physics, Illinois Institute of Technology, Chicago, IL, 60616, USA

a r t i c l e i n f o a b s t r a c t

Article history: Peak fitting is an essential part of X-ray photoelectron spectroscopy (XPS) narrow scan analysis, and the
Received 31 January 2016 Literature contains both good and bad examples of peak fitting. A common cause of poor peak fitting
Received in revised form 9 June 2016 is the inclusion of too many fit parameters, often without a sound chemical and/or physical basis for
Accepted 10 June 2016
them, and/or the failure to reasonably constrain them. Under these conditions, fit parameters are often
Available online 15 June 2016
correlated, and therefore lacking in statistical meaning. Here we introduce the uniqueness plot as a
simple graphical tool for identifying bad peak fits in XPS, i.e., fit parameter correlation. These plots are
Keywords:
widely used in spectroscopic ellipsometry. We illustrate uniqueness plots with two data sets: a C 1s
X-ray photoelectron spectroscopy
XPS
narrow scan from ozone-treated carbon nanotube forests and an Si 2p narrow scan from an air-oxidized
Uniqueness plot silicon wafer. For each fit, we consider different numbers of parameters and constraints on them. As
Correlation expected, the uniqueness plots are parabolic when fewer fit parameters and/or more constraints are
Fit parameters applied. However, they fan out and eventually become horizontal lines as more unconstrained parameters
Spectroscopic ellipsometry are included in the fits. Uniqueness plots are generated by plotting the chi squared (␹2 ) value for a fit vs.
a systematically varied value of a parameter in the fit. The Abbe criterion is also considered as a figure of
merit for uniqueness plots in the Supporting Information. We recommend that uniqueness plots be used
by XPS practitioners for identifying inappropriate peak fits.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
X-ray photoelectron spectroscopy (XPS) is a widely used surface
characterization technique; it is currently mentioned in approxi-
mately 10,000 publications per year [1–3]. XPS uses peak positions
and peak shapes to provide the identities and chemical states of
the elements at surfaces. Because both the natural line widths of
XPS signals and their chemical shifts are on the order of 1 eV, peak
fitting is an essential part of XPS data analysis [4,5]. However, peak
fitting can be a subjective and challenging exercise [6]. For exam-
ple, Wepasnick and coworkers fit a C 1s narrow scan from oxidized
carbon nanotubes (CNTs) using parameters from two previously
published fits [7–9]. In both cases, the overall fits were good. How-
ever, the fraction of the carboxyl, C(III) [10], signal in the fits differed
drastically: ca. 6% vs. 11.0%.
∗ Corresponding author at: Department of Chemistry and Biochemistry, C-306,
Benson Bldg., Brigham Young University, Provo, UT, 84602.
E-mail address: mrlinford@chem.byu.edu (M.R. Linford).
There are a number of possible pitfalls in XPS peak fitting. These
include (i) adding too many unconstrained peaks or fit parameters,
often without a reasonable chemical or physical basis for them,
(ii) using inappropriate backgrounds, (iii) failing to show the sum-
mation of ones fit components, and (iv) failing to demonstrate the
statistical quality of one’s fit with chi squared (␹2 ), the reduced
chi squared (␹2* ), the Abbe criterion, etc [11,12]. When too many
parameters can vary (float) in a fit, they are often correlated, which
means they lack statistical meaning. In XPS, the degree of cor-
relation can be identified through the Hessian matrix, H, where
parameters are correlated if the mixed partial derivatives of ␹2 (the
off-diagonal elements of this matrix) are non-zero [11]. We recently
introduced the equivalent width and autocorrelation width as less
biased figures of merit for XPS narrow scans [13,14]. These width
functions are sensitive to chemical changes in materials.
Spectroscopic ellipsometry (SE) data analysis does not involve
peak fitting per se. However, SE and XPS data analysis are simi-
lar in that both generally involve fitting multiple components and
parameters. In both cases, correlation occurs when a large num-
ber of fit parameters are employed. In essence, ‘correlation’ means

http://dx.doi.org/10.1016/j.apsusc.2016.06.070
0169-4332/© 2016 Elsevier B.V. All rights reserved.
156 B. Singh et al. / Applied Surface Science 387 (2016) 155–162
Fig. 1. Uniqueness plots for spectroscopic ellipsometry data showing the MSE
(error) as a function of the fixed SiO2 layer thickness of an Si/SiO2 sample. The first
approach (top, circles) involves reasonable constraints on the fit parameters. In the
second approach (bottom, triangles) the fit parameters are unconstrained.
that when a particular parameter varies, other fit parameters can
change in a compensatory way, giving the same error to the fit.
The SE and XPS communities are well aware of the mathemati-
cal calculation of fit parameter correlation, including the parabolic
relationship that is often found between chi squared and a given
fit parameter [11,15,16]. However, in the SE community, correla-
tion is commonly identified through uniqueness plots, which are
graphical tools that can be easily interpreted [17–19].
In a uniqueness plot, the error to the fit is plotted as a function
of one of the variables (fit parameters), where this parameter is
repeatedly fixed to different values about its optimal value, and the
remaining fit parameters are allowed to vary. If the error in the fit
rises as the parameter in question is varied, in general in a parabolic
fashion [11], the fit is unique. However, if the fit parameter can be
systematically varied and the error of the fit stays constant, there is
no ‘uniqueness’. That is, if any value of the parameter gives the same
result/error, the fit parameter, and therefore fit, are meaningless.
Fig. 1 shows an SE uniqueness plot. It was derived from SE data
collected from a ca. 500 nm film of silicon dioxide (SiO2 ) on silicon.
The data were modeled in standard fashion [20,21] using four lay-
ers: (i) the silicon substrate, (ii) an Si/SiO2 interface layer, (iii) the
SiO2 film, and (4) a roughness layer. In the first approach, reasonable
constraints were applied to the model, e.g. the optical constants of
the Si substrate were taken from the instrument software and fixed,
the thickness of Si/SiO2 interface layer was fixed and its optical
constants were taken from the software, etc. Using this approach,
which had a sound chemical and physical basis, the optimal thick-
ness of the SiO2 layer was found to be 511 nm (see Supporting
Information for additional details.) We probed the uniqueness of
this result by varying and fixing the thickness of the SiO2 film about
this value (from 500 to 530 nm), recording the mean square error
(MSE) of the fit at each constrained value of the thickness. Fig. 1
shows the resulting parabolic uniqueness plot. This plot implies a
unique result because the errors increase as we vary the thickness
of the SiO2 layer from its optimal value. That is, we obtain here the
favorable result that the other parameters in the model are unable
to compensate for forced changes in the SiO2 film thickness. In a
second approach, the model was unconstrained, i.e., all the param-
eters floated. Fig. 1 shows a non-unique result here – a horizontal
line. That is, the same low error is obtained when the film thick-
ness is systematically set to a wide range of values. We conclude
that because the error of the fit does not change when the thick-
ness of the SiO2 layer is varied, the fit has no statistical meaning.
Clearly, the uniqueness plots in Fig. 1 constitute a straightforward
and useful graphical tool that can aid novice and experienced SE
practitioners alike to pinpoint unreasonable fits. Again, a parabolic
result implies uniqueness, while an excessively broad parabola or
a horizontal line indicates statistically meaningless results.
Here we propose the use of uniqueness plot to identify inap-
propriate XPS peak fits. There is a need for this tool because of the
increased popularity of the technique – an increasing number of
untrained individuals are collecting and analyzing XPS spectra [2,3].
Nevertheless, uniqueness plots should be valuable to inexperienced
and experienced practitioners alike. Less skilled users will quickly
identify unconstrained, inappropriate models, and those that are
more experienced will quickly confirm that their models are more
reasonable. Uniqueness plots are most useful in identifying poor
peak fits, as opposed to better ones. Of course mathematical fit-
ting alone is an insufficient criterion for the quality of an analysis.
Models should always be implemented and constrained based on
a priori chemical and physical knowledge about a system and Lit-
erature precedent.
To demonstrate uniqueness plots in XPS, we fit two different
narrow scans: the C 1s spectrum of an ozone-treated carbon nan-
otube forest (CNT) and the Si 2p spectrum from an air-oxidized
silicon substrate. Here, parabolic plots are obtained when a limited
number of fit parameters are employed and more shallow curves,
or horizontal lines, when larger numbers of unconstrained parame-
ters are allowed. Both reduced chi squared (␹2* ) and Abbe criterion
values were explored in these plots. The chi squared-based unique-
ness plots appear to be easier to interpret. The Abbe criterion results
are reported in the Supporting Information. The uniqueness plot is a
standard feature of SE data analysis software. We recommend that
vendors of XPS analysis software similarly introduce uniqueness
plots. (One of the authors of this paper has already implemented a
feature that is somewhat similar to uniqueness plots into a com-
mercial XPS software package [22].) However, special software is
not necessary to prepare uniqueness plots. Those shown herein
were prepared with our instrument software that does not offer
this particular feature.
2. Experimental
Two sets of XPS data were employed in this study:
1. A C 1s narrow scan from an ozone-treated carbon nanotube
(CNT) forest with an oxygen content of 3.7 at.% by XPS. This CNT
spectrum was collected as part of a study on infiltrated, CNT-
templated thin layer chromatography plates [23–25]. Note that
this spectrum was taken with an older spectrometer, and that
the sample is inherently complex. Accordingly, it is somewhat
challenging to resolve/describe all the components in it. A more
advanced approach here would probably include accounting for
asymmetry in the line shapes and using somewhat different peak
widths for the different components per literature reports [26].
Nevertheless, the current fit seems sufficient to illustrate unique-
ness plots.
2. An Si 2p narrow scan of a native-oxide terminated silicon shard
[27,28] (ca. 1.5 × 1.5 cm2 ). It was air oxidized for one minute at
900 ◦ C in a ThermolyneTM benchtop muffle furnace from Thermo
Scientific. The resulting oxide layer was 3.58 nm by SE. The opti-
cal constants of Si and SiO2 for the SE modeling were obtained
from the instrument software. Because this spectrum was col-
lected with an older instrument, it was not possible to resolve
the 2p3/2 − 1/2 doublet. But again, this spectrum seems adequate
to illustrate the concepts we introduce herein.
XPS analyses were performed with a Surface Science SSX-100 X-
ray photoelectron spectrometer (serviced by Service Physics, Bend,
OR) with a monochromatic Al K␣ source (1486.7 eV) and a hemi-
spherical analyzer. Narrow scans were recorded with a spot size
 B. Singh et al. / Applied Surface Science 387 (2016) 155–162
of 500 ␮m × 500 ␮m, resolution: 3 (nominal pass energy 100 eV),
number of scans: 20, and step size of 0.065 eV. The CNT spectrum
was referenced to the main C 1s peak in the narrow scan, which
was taken at 284.6 eV, and the silicon spectrum was referenced to
the O 1s peak taken at 532.0 eV. This latter signal appeared as a
single, shoulderless peak. Peak fitting was performed in our instru-
ment software (‘ESCA Data Analysis’ version V5.01.02), and fits
were optimized based on a minimization of the ␹2* value. Shirley
type backgrounds [29] were used for all the fits.
SE data were collected from ca. 200–1700 nm with an M-2000
instrument from the J.A. Woollam Co., Lincoln, NE. For Fig. 1, the
data were range selected from 300 to 400 nm. The time necessary
for the software to generate a uniqueness plot was excessively long
when a wider wavelength window was used with an unconstrained
model.
2.1. Theory of error estimation tools
The error estimation tools employed herein are the reduced chi
squared (␹2* ) and Abbe criterion values. Hesse has described these
error estimation tools in detail [11,12] which help determine the
quality of a fit vis-à-vis the difference between the experimental
data and the modeled (fit) envelope. The fit envelope is the sum of
the individual fit components in a model.
The chi squared value is defined as follows:
N   2
   
M (i) − S i, p
2  =
p (1)
M (i)
i=1
 ) refer to the values of the experimental data
Where, M(i) and S(i, p
and fit at a given point, respectively. The vector, p  , contains the fit
parameters used in the model. The difference between the experi-
mental data and fit envelope is squared at each data point and then
normalized to the value of experimental data point. The reduced
chi squared value is defined as:
 
  
2 p
 =
2∗ p (2)
N−P
where N is the number of data points and P is the number of fit
parameters employed.
Obviously, a lower value of ␹2 or ␹2* implies a better fit. How-
ever, as Sherwood clarified [4], ␹2 is of greatest value when it is
reported for a series of peak fits on the same spectrum, or when
applied to similar spectra.
 ) − M(i).
The residuals, R(i), of a fit are given by S(i,p
The Abbe criterion is defined as:
N−1 2
1 [R (i + 1) − R (i)]
i=1
Abbe =
2
N 2
(3)
i=1 [R (i)]
Where R(i + 1) and R(i) refer to the residuals at the (i + 1)th and ith
data points, respectively. An Abbe criterion of zero indicates that
the fit envelope consistently misses the experimental peak enve-
lope by the same amount, i.e., R(i) = R(i + 1). An Abbe criterion value
of two is obtained for anti-correlated residuals. The Abbe criterion
is unity when the residuals are statistically distributed as random
noise. This is the ideal case.
Of course it is vital to use common sense and a priori knowl-
edge when peak fitting XPS narrow scans [4,12,26], e.g., one should
not ignore earlier measurements on similar systems. For example,
while it is possible you will find unknown species by XPS when you
oxidize silicon, it is unlikely.
157
3. Results and discussion
To show the usefulness of uniqueness plots in XPS, we peak
fitted narrow scans in a constrained and unconstrained fashion.
As expected, when the number of unconstrained fit parameters
increases, the uniqueness of the fits decreases.
3.1. Ozone-treated CNT sample (varying C-C peak width)
A reasonable peak fit to a C 1s narrow scan of ozone-treated
CNTs was obtained by introducing peaks that represent: (i) carbon
bonded to carbon and hydrogen (C-C), where this peak was initially
placed at ca. 284.6 eV, but then allowed to float – it had a vari-
able position of x eV, (ii) carbon bonded to one oxygen atom (C-O)
at x + 1.5 eV, (iii) carbonyl carbon (C O) at x + 2.7 eV, and (iv) car-
boxyl carbon (O C O) at x + 3.9 eV. These peaks can be designated
by their oxidation states: C(0), C(I), C(II), and C(III), respectively
[13]. As appropriate for an aromatic material, a shake-up peak at
x + 6.5 eV was also included. All peak widths were constrained to the
same value, except the shake-up peak, which had twice this width.
The Voigt function, a convolution of a Gaussian and a Lorentzian,
is the ideal function for modeling XPS narrow scans [5]. However,
pseudo-Voigt functions (Gaussian:Lorentzian (G:L) sum or product
functions) are also commonly used in XPS peak fitting. Of the two,
the G:L product function is less effective [5,30]. The only option in
our software at BYU is the G:L sum function. All the peaks mod-
eled herein had symmetric G:L sum functions and the same G:L
ratio, unless otherwise specified. The heights of the peaks floated.
Of course all these assignments are semi-empirical. Fig. 2a shows
the optimal fit obtained through this approach, which gave a C-C
peak width of 1.37 eV and a G:L ratio of 93%.
In a uniqueness plot, one fit parameter is systematically fixed to
different values about its optimal value, while the other adjustable
parameters vary to obtain the best possible fit. This is illustrated
graphically in Fig. 2a–d. Fig. 2a shows the width of the C-C peak
at its optimal value of 1.37 eV in a fit. In Fig. 2c–d, this peak width
was fixed to other values and a new fit was performed. For these
latter fits, the only parameter that floated was the G:L ratio of the
C-C peak – obviously one would not expect changes in this ratio
to compensate for the large changes in the C-C peak width shown
in the figure. The lack of fit in Fig. 2b–d, is shown in the residuals,
which clearly increase as the system diverges from the optimal C-C
width. This system appears to be unique.
A more quantitative way of describing the quality of the fits
in Fig. 2 is through ␹2* and/or Abbe criterion values in unique-
ness plots. Fig. 3 shows a plot of ␹2* vs. C-C peak width (the black
squares) for the series of fits that is partially shown in Fig. 2. Here,
the C-C peak widths were systematically varied from 0.8 to 2.0 eV.
The parabolic shape of this uniqueness plot (the ‘Approach 1’ data)
is consistent with uniqueness, and therefore statistical meaning,
to the C-C peak width and model used in Fig. 2. As expected, the
minimum error (␹2* value) is obtained at the optimal value of the
C-C peak width. Uniqueness plots based on the Abbe criterion are
shown in the Supporting Information. They tend to be inversely
related to the plots based on reduced chi squared values.
To further show the use of uniqueness plots in XPS, the con-
straints on the fit/approach in Fig. 2 were increasingly relaxed (see
Table 1). The resulting uniqueness plots are presented in Fig. 3.
Here, the general result is that as the constraints are removed, the
curves become increasingly flat, fanning out and showing less cur-
vature, while the minimum ␹2* value drops somewhat. Finally, with
no constraints (Approach 8), a horizontal line is obtained (dark
green hexagons). This flat line, like the one in Fig. 1, indicates
that the C-C peak width can be varied over a wide range of val-
ues, and the other fit parameters can compensate for any change
in it, always yielding the same, low error. For this unconstrained
158 B. Singh et al. / Applied Surface Science 387 (2016) 155–162

Fig. 2. (a) Peak fitting of a C 1s narrow scan of ozone-treated CNTs obtained using the most constrained approach in Table 1 (Approach 1) showing the optimal C-C peak
width value of 1.37 eV. (b–d) Poorer peak fits, also from Approach 1, for constrained C-C peak widths of 1.00, 1.20, and 1.90 eV, respectively. Black traces at the top of each
panel are residuals to the fits.

Table 1
Fitting approaches used to generate the eight uniqueness plots in Fig. 3. The number of fixed parameters decreases proceeding down the table. Fits were to the C 1s spectrum
of ozone-treated CNTs shown in Figs. 2 and 4, and the corresponding uniqueness plots are based on varying the width of the C-C peak.

Approach Fixed Floated in the Fit

1 All peak positions, peak widths, peak heights Gauss% of C-C peak
and Gauss% (except C-C Gauss%)
2 All peak positions, peak widths, and peak Gauss% of all peaks
heights
3 All peak positions, peak widths, and peak Gauss% of all peaks, and peak height of C-C
heights (except C-C peak) peak
4 All peak positions, and peak widths Gauss% and peak heights of all peaks
5 All peak positions, and peak widths (except Gauss%, peak heights of all peaks, and peak
shake-up peak) width of shake-up peak
6 All peak positions Gauss%, peak heights, and peak widths of all
peaks
7 All peak positions (except C-C peak) Gauss%, peak heights, and peak widths of all
peaks, peak position of C-C peak
8 Nothing All Gauss%, peak heights, all peak positions,
and all peak widths

parameters, e.g., its minimum value of ␹2* is lower, it is not chemi-

Fig. 3. Uniqueness plots for the C 1s narrow scan of ozone-treated CNTs using the
eight approaches described in Table 1. See also Figs. 2 and 4. Reduced chi squared
values are plotted against the C-C peak width, which was fixed to specific values.
(For interpretation of the references to colour in the text, the reader is referred to
the web version of this article.)
approach, the C-C peak width, and presumably all the other fit
parameters, lack any statistical meaning. We emphasize that while
the unconstrained fit is numerically superior to the fits with fewer
cally or physically reasonable. It is necessary to fit with reasonably
constrained parameters that have a solid physical/chemical basis.
To graphically illustrate the unpleasant consequences of uncon-
strained peak fitting, Fig. 4 shows four examples of peak fitting
using Approach 8 in Table 1 (the unconstrained approach). These
four fits show equally low ␹2* values, but significantly different
peak/fit components. In general, the positions and widths of the
peaks in these fits are unreasonable even though, numerically
speaking, the low residuals here are ‘better’ than those in Fig. 2 –
they are lower. For example, it is difficult to imagine how the very
different widths of the light blue and dark blue peaks in Fig. 4b
could be chemically justified. Variation in peak width is generally
only observed in highly disordered materials and then only with
small variation in those peak widths [31–33]. The shake-up signals
have also become excessively broad in these spectra.
3.2. Ozone-treated CNT sample (varying C-O peak position)
To further illustrate the properties of uniqueness plots, we peak
fitted the same C 1s narrow scan of oxidized CNTs used in the previ-
ous example, while varying the C-O peak position (see Fig. 5). Eight
peak fitting approaches were also considered here (see Table 2),
which ranged from most constrained (Approach 1) to least con-
 B. Singh et al. / Applied Surface Science 387 (2016) 155–162 159

Fig. 4. (a) Peak fitting of a C 1s narrow scan of ozone-treated CNTs obtained using the least constrained approach in Table 1 (Approach 8) showing the optimal peak width
value of 1.37 eV. (b–d) Equally unreasonable peak fits for constrained C-C peak widths of 1.00, 1.20, and 1.90 eV, respectively. Black traces at the top of each panel are residuals
to the fits. (For interpretation of the references to colour in the text, the reader is referred to the web version of this article.)

Table 2
Approaches used to generate the eight uniqueness plots in Fig. 5. The number of fixed parameters decreased from Approach 1 to Approach 8. All fits were to the C 1s spectrum
of ozone-treated CNTs shown in Figs. 2 and 4, and are based on changing and fixing the position of the C-O peak.

Approach Fix Float

1 All peak positions, peak widths, peak heights Gauss% of C-O peak
and Gauss% (except C-O Gauss%)
2 All peak positions, peak widths, and peak Gauss% of all peaks
heights
3 All peak positions, peak widths, and peak Gauss% of all peaks, and peak height of C-C
heights (except C-C peak) peak
4 All peak positions, and peak widths Gauss% and peak heights of all peaks
5 All peak positions, and peak widths (except Gauss%, peak heights of all peaks, and peak
C-C) width of C-C peak
6 All peak positions Gauss%, peak heights, and peak widths of all
peaks
7 All peak positions (except shake-up peak) Gauss%, peak heights, and peak widths of all
peaks, peak position of shake-up peak
8 Nothing All Gauss%, peak heights, all peak positions,
and all peak widths

in increments of 0.05 eV, and the ␹2* and Abbe criterion values
were calculated at each of these values. As expected, the most con-
strained approach yielded the curve (parabola) with the highest
curvature. As the constraints were relaxed, the uniqueness plots
showed less curvature, fanning out. The unconstrained approach
in Table 2 (Approach 8) showed the lowest ␹2* value with very
low curvature. These results again illustrate that in unconstrained
models the fit parameters lack statistical meaning.

3.3. Si 2p narrow scan fit to two peaks [34]: varying the SiO2

peak width

The Si 2p spectrum in Fig. 6 of an air-oxidized silicon wafer was

Fig. 5. Uniqueness plots for the fits to a C 1s narrow scan of ozone-treated CNTs
using the eight approaches described in Table 2 (See also Figs. 2 and 4). The reduced
chi squared values for the fits are plotted against the C-O peak position, which was
fixed to specific values.
strained (Approach 8). The optimal C-O peak position obtained from
Approach 1 in Table 1 was used: 286.07 eV (see Fig. 2a). In these fits,
the C-O peak position was systematically fixed at 285.50–286.50 eV
initially fit to two peaks: one corresponding to the bulk Si material
(at ca. 99 eV), and the other to the SiO2 film (at ca. 103 eV). The G:L
ratios of these peaks varied independently. The optimal peak width
of the SiO2 peak (1.84 eV) was 1.35 times the width of bulk Si peak,
which is in accord with literature reports [4]. The purpose of this
initial fit was to obtain values about which the fit parameters could
be varied in uniqueness plots. Six uniqueness plots were generated
using the approaches listed in Table 3 in which the SiO2 peak width
was varied from 1.00–2.20 eV in increments of 0.05 eV. Fig. 7 shows
the resulting uniqueness plots (␹2* vs. SiO2 peak width). Interest-
ingly, but not surprisingly, uniqueness is obtained for all seven
160 B. Singh et al. / Applied Surface Science 387 (2016) 155–162
Table 3
Approaches used to generate the six uniqueness plots in Fig. 7. The number of fixed parameters decreased from Approach 1 to Approach 6. All fits were to an Si 2p spectrum
from a sample of air-oxidized silicon (see Fig. 6), and are based on varying the width of the SiO2 peak.
Approach Fix
1 All peak positions, peak widths, and peak
heights
2 All peak positions, peak widths, and peak
heights (except SiO2 peak)
3 All peak positions, and peak widths
4 All peak positions, and peak widths (except Si
peak)
5 Peak position of Si peak
6 Nothing
Fig. 6. Optimal fit to an Si 2p narrow scan using two components: a bulk Si and an
oxidized Si peak.
Fig. 7. Uniqueness plots for the fits to an Si 2p narrow scan of an oxidized silicon
wafer (see Fig. 6). The reduced chi squared values are plotted against a fit parameter
(the SiO2 peak width) that was fixed to specific values.
approaches. That is, fitting a Si 2p XPS peak envelope that has two
obvious components to two peak components significantly limits
the options for getting unreasonable results. Here, the most con-
strained approach (Approach 1) gives the most unique results, e.g.,
the tightest parabola-like curve in Fig. 7, while the less constrained
approaches (Approaches 2–6) give the somewhat broader curves.
Very similar results were obtained from an analysis in which the
bulk Si peak width was systematically varied.
Float
Gauss% of all peaks
Gauss% of all peaks and peak height of SiO2
peak
Gauss% and peak heights of all peaks
Gauss% and peak heights of all peaks, and peak
width of Si peak
Gauss% and peak heights of all peaks, peak
width of Si peak, and peak position of SiO2 peak
All Gauss%, peak heights, all peak positions and
peak widths
Fig. 8. Optimal fit to an Si 2p narrow scan using five components: a bulk Si peak and
four oxidized Si peaks denoted Six+ , with x = 1–4. This fitting approach is adapted
from Himpsel et al. [17].
3.4. Si 2p narrow scan fit to five peaks: varying the Si2+ peak
width
In this example, the Si 2p spectrum in Fig. 6 was fit to five peaks
(see Fig. 8). These correspond to a bulk Si peak (the peak at lowest
binding energy), and four peaks that represent various forms of oxi-
dized silicon. Himpsel et al. designated the peak corresponding to
fully oxidized silicon in SiO2 as ‘Si4+ ’, and the peaks corresponding
to less oxidized silicon (suboxides) as Si1+ , Si2+ , and Si3+ [34,35]. In
the initial, reasonable, fit to the narrow scan, the bulk Si peak and
Si4+ positions were allowed to float, while the peak positions of
the Si1+ , Si2+ and Si3+ components were constrained, per Himpsel’s
work, to be +0.95, +1.75, and + 2.48 eV from the bulk Si peak posi-
tion. Initially the G:L ratios of all the peaks floated, and the best
fit was obtained when the peaks were modelled with 100% Gaus-
sians − the G:L ratios of the peaks were fixed to this value. The peak
widths of the Si bulk peak and Si1+ signal were allowed to float, and
the widths of the Si2+ , Si3+ , and Si4+ peaks were constrained to have
the same values as the Si1+ peak, as reported in Himpsel’s work. All
peak heights floated. From this fit, the optimal peak width of the
Si4+ peak was 1.89 eV.
Uniqueness plots were obtained using the six approaches
described in Table 4 (see Fig. 9). In these plots, the width of the
Si4+ peak was systematically varied from 1.5 to 2.5 eV in incre-
ments of 0.05 eV. The trends are similar to what was observed in
the previous examples. The uniqueness plots fanned out and flat-
tened as the number of fit parameters increased (Fig. 9), with the
least constrained approach showing nearly a horizontal line.
 B. Singh et al. / Applied Surface Science 387 (2016) 155–162 161

Table 4
Approaches used to generate the six uniqueness plots in Fig. 9. The number of fixed parameters decreased from Approach 1 to Approach 6. All fits were to the Si 2p spectrum
from a sample of air-oxidized silicon (see Figs. 6 and 8), and are based on varying the width of the Si4+ peak.

Approach Fix Float

1 All peak positions, peak widths, and peak Gauss% of all peaks
heights
2 All peak positions, peak widths, and peak Gauss% of all peaks and peak height of Si4+ peak
heights (except Si4+ peak height)
3 All peak positions, and peak widths Gauss% and peak heights of all peaks
4 All peak positions All Gauss%, peak heights, and peak widths
5 All peak positions, except Si3+ peak Gauss%, peak heights, and peak widths of all
peaks, and peak position of Si3+ peak
6 Nothing All Gauss%, peak heights, all peak positions and
peak widths

not remove from the analyst the need to read and understand the
related literature, seek expert advice, use restraint/common sense
in designing a model, etc. We recommend that uniqueness plots be
used in XPS peak fitting efforts.

Acknowledgements

We acknowledge the Department of Chemistry and Biochem-

istry and College of Physical and Mathematical Sciences at Brigham
Young University for their support of this work.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.06.
Fig. 9. Uniqueness plots for the fits to a Si 2p narrow scan from an oxidized silicon
070.
wafer using the six approaches described in Table 4. See also Fig. 8. Reduced chi
squared values are plotted against the Si4+ peak width (a fit parameter) that was
fixed to specific values. References

[1] C.J. Powell, J. Vac. Sci. Technol. A 21 (5) (2003) S42–S53.

[2] C.J. Powell, J. Surf. Anal. 20 (2014).
3.5. Quantitation of errors from uniqueness plots [3] B. Singh, M.R. Linford, Vac. Technol. Coat. (October) (2015).
[4] P.M.A. Sherwood, J. Vac. Sci. Technol. A 14 (3) (1996) 1424–1432.
The SE community has made some attempt to quantify errors [5] M.R. Linford, Vac. Technol. Coat. (July) (2014) 27–33.
[6] B.V. Crist, J. Surf. Anal. 4 (3) (1998) 428–434.
from uniqueness plots. For example, Hilfiker et al. noted: “It is
[7] K.A. Wepasnick, B.A. Smith, J.L. Bitter, D.H. Fairbrother, Anal. Bioanal. Chem.
also convenient to record the parameter range that maintains MSE 396 (3) (2010) 1003–1014.
results within 10% (or any arbitrary percentage) of the minimum [8] M. Li, M. Boggs, T.P. Beebe, C.P. Huang, Carbon 46 (3) (2008) 466–475.
[9] H. Wang, A. Zhou, F. Peng, H. Yu, J. Yang, J. Colloid Interface Sci. 316 (2) (2007)
value. This parameter range will be referred to as the Unique-
277–283.
ness Range.” [17] Clearly this approach could be used to estimate [10] V. Gupta, H. Ganegoda, M.H. Engelhard, J. Terry, M.R. Linford, J. Chem. Educ. 91
XPS peak fit parameter uncertainty, and it may be the subject of (2) (2013) 232–238.
our future study on this topic. However, here we have presented [11] R. Hesse, T. Chasse, P. Streubel, R. Szargan, Surf. Interface Anal. 36 (10) (2004)
1373–1383.
the uniqueness plot as a tool for identifying inappropriate, uncon- [12] B. Singh, R. Hesse, M.R. Linford, Vac. Technol. Coat. (December) (2015).
strained XPS peak fits. We believe that this meets the greatest [13] B. Singh, D. Velázquez, J. Terry, M.R. Linford, J. Electron Spectrosc. 197 (0)
current need in the community. (2014) 56–63.
[14] B. Singh, D. Velázquez, J. Terry, M.R. Linford, J. Electron Spectrosc. 197 (0)
(2014) 112–117.
[15] M.M. Ibrahim, N.M. Bashara, J. Opt. Soc. Am. 61 (12) (1971) 1622–1629.
4. Conclusions
[16] G.H. Bu-Abbud, N.M. Bashara, J.A. Woollam, Thin Solid Films 138 (1) (1986)
27–41.
Uniqueness plots are simple and straightforward graphical tools [17] J.N. Hilfiker, N. Singh, T. Tiwald, D. Convey, S.M. Smith, J.H. Baker, H.G.
Tompkins, Thin Solid Films 516 (22) (2008) 7979–7989.
that XPS practitioners can use to flag inappropriate peak fits. In
[18] G. Droulers, A. Beaumont, J. Beauvais, D. Drouin, J. Vac. Sci. Technol. B 29 (2)
uniqueness plots, the degree of curvature of the parabolic curves is (2011) 021010.
proportional to the uniqueness of the fit – a high degree of curva- [19] J.M. Zhao, P. Yang, Microsyst. Technol. 18 (9–10) (2012) 1455–1461.
ture implies a unique fit, and a lower degree of curvature implies [20] C.M. Herzinger, B. Johs, W.A. McGahan, J.A. Woollam, W. Paulson, J. Appl.
Phys. 83 (6) (1998) 3323–3336.
a fit in which there is a higher degree of fit parameter correla- [21] V.A. Yakovlev, E.A. Irene, J. Electrochem. Soc. 139 (5) (1992) 1450–1455.
tion. At the extreme of parameter correlation a horizontal line is [22] http://www.rdataa.com/AAnalyzer.
obtained, which is a strong indicator of an inappropriate peak fit. [23] D.S. Jensen, S.S. Kanyal, N. Madaan, A.J. Miles, R.C. Davis, R. Vanfleet, M.A. Vail,
A.E. Dadson, M.R. Linford, J. Vac. Sci. Technol. B 31 (3) (2013).
For relatively simple narrow scans that can be modeled with few [24] J. Song, D.S. Jensen, D.N. Hutchison, B. Turner, T. Wood, A. Dadson, M.A. Vail,
components, the chances of generating unreasonable peak fits are M.R. Linford, R.R. Vanfleet, R.C. Davis, Adv. Funct. Mater. 21 (6) (2011)
low. We emphasize again that while uniqueness plots are impor- 1132–1139.
[25] D.S. Jensen, S.S. Kanyal, V. Gupta, M.A. Vail, A.E. Dadson, M. Engelhard, R.
tant and valuable because they spot bad fits, they do not identify or Vanfleet, R.C. Davis, M.R. Linford, J. Chromatogr. A 1257 (2012) 195–203.
confirm good ones. That is, while passing a uniqueness test is cer- [26] H. Ganegoda, D.S. Jensen, D. Olive, L.D. Cheng, C.U. Segre, M.R. Linford, J. Terry,
tainly an important step towards obtaining a good peak fit, it does J. Appl. Phys. 111 (5) (2012).
162 B. Singh et al. / Applied Surface Science 387 (2016) 155–162
[27] D.S. Jensen, S.S. Kanyal, N. Madaan, M.A. Vail, A.E. Dadson, M.H. Engelhard,
M.R. Linford, Surf. Sci. Spectra 20 (1) (2013) 36–42.
[28] S.S. Kanyal, D.S. Jensen, Z. Zhu, M.R. Linford, Surf. Sci. Spectra 22 (2) (2015)
1–6.
[29] D.A. Shirley, Phys. Rev. B 5 (12) (1972) 4709–4714.
[30] R. Hesse, P. Streubel, R. Szargan, Surf. Interface Anal. 39 (5) (2007) 381–391.
[31] R.J. Cole, P. Weightman, J. Phys.: Condens. Matter 10 (25) (1998) 5679.
[32] W. Olovsson, T. Marten, E. Holmström, B. Johansson, I.A. Abrikosov, J. Electron
Spectrosc. 178–179 (0) (2010) 88–99.
[33] T. Marten, W. Olovsson, S.I. Simak, I.A. Abrikosov, Phys. Rev. B 72 (5) (2005)
054210.
[34] F.J. Himpsel, F.R. McFeely, A. Taleb-Ibrahimi, J.A. Yarmoff, G. Hollinger, Phys.
Rev. B 38 (9) (1988) 6084–6096.
[35] A. Herrera-Gomez, F.-S. Aguirre-Tostado, P. Pianetta, J. Vac. Sci. Technol. A 34
(2) (2016) 020601.