Practical Guide For Curve Fitting in XPS

Practical guide for curve fitting in x-ray
photoelectron spectroscopy
Cite as: J. Vac. Sci. Technol. A 38, 061203 (2020); https://doi.org/10.1116/6.0000377
Submitted: 05 June 2020 • Accepted: 18 September 2020 • Published Online: 06 October 2020
George H. Major, Neal Fairley, Peter M. A. Sherwood, et al.
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Paper published as part of the special topic on Special Topic Collection: Reproducibility Challenges and Solutions
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© 2020 Author(s).
TUTORIAL avs.scitation.org/journal/jva
Practical guide for curve fitting in x-ray

photoelectron spectroscopy
Cite as: J. Vac. Sci. Technol. A 38, 061203 (2020); doi: 10.1116/6.0000377
Submitted: 5 June 2020 · Accepted: 18 September 2020 · View Online Export Citation CrossMark
Published Online: 6 October 2020
George H. Major,1 Neal Fairley,2 Peter M. A. Sherwood,3 Matthew R. Linford,1 Jeff Terry,4 Vincent Fernandez,5
and Kateryna Artyushkova6,a)
AFFILIATIONS
1
Department of Chemistry and Biochemistry, Brigham Young University, C100 BNSN, Provo, Utah 84602
2
Casa Software Ltd., Bay House, Teignmouth, United Kingdom
3
Department of Chemistry, University of Washington, Seattle, Washington 98195
4
Illinois Institute of Technology, 3101 S. Dearborn St., Chicago, Illinois 60616
5
CNRS, Institut des Matériaux Jean Rouxel, IMN, Université de Nantes, F-44000 Nantes, France
6
Physical Electronics, 18725 Lake Drive East, Chanhassen, Minnesota 55317
Note: This paper is part of the Special Topic Collection on Reproducibility Challenges and Solutions.
a)
Electronic mail: [email protected]
ABSTRACT
The use of peak fitting to extract information from x-ray photoelectron spectroscopy (XPS) data is of growing use and importance. Due to
increased instrument accessibility and reliability, the use of XPS instrumentation has significantly increased around the world. However, the
increased use has not been matched by the expertise of the new users, and the erroneous application of curve fitting has contributed to
ambiguity and confusion in parts of the literature. This guide discusses the physics and chemistry involved in generating XPS spectra,
describes good practices for peak fitting, and provides examples of appropriate use along with tools for avoiding mistakes.
Published under license by AVS. https://doi.org/10.1116/6.0000377
I. INTRODUCTION Curve fitting, also known as peak fitting,4 is the process used
Over the past 30 years, x-ray photoelectron spectroscopy (XPS) to extract information from the spectral data for a number of tech-
has become the most widely used surface analysis tool and has been niques. Although the details of curve fitting depend on the techni-
an essential component of many research studies.1 Curve fitting has que in question, the curve fitted spectra generally contain
been widely used for more than 50 years for extracting chemical overlapping peaks. Each of these peaks is represented by a function
information from the overlapping features in high-resolution XPS that reflects the physical process involved in generating the original
spectra.2 Despite computational advances and higher accessibility of signal. XPS data interpretation and representation range from a
software resources, it has been challenging to develop a chemically rudimentary understanding/extraction of the elements present in a
and physically meaningful approach to curve fitting. The absence of material to advanced peak fitting and background analysis that
a distinct theoretical description of XPS fitting has led to the publica- reveal chemical states and sample morphologies.
tion of erroneous conclusions about surface chemistry.2,3 In an In XPS, it is convenient to identify two spectral regions,
ongoing study of XPS data in three high profile journals,3 it was namely, the core region (electrons with binding energies, BEs,
observed that roughly 70% of the papers using XPS analyzed the greater than 30 eV) and the valence band region (BE < 30 eV). In
data using some type of curve fitting. Furthermore, errors, miscon- the core region, the spectral features arise from photoelectrons gen-
ceptions, and bad curve-fitting practices accounted for most of the erated from core energy levels (atomic orbitals), which are charac-
serious problems in both the measured XPS data and the spectral teristic of the individual atoms in the sample.5 In contrast, the
analysis that were identified in more than 30% of the papers ana- features in the valence band region arise from photoelectrons
lyzed. This guide is intended to help address this important problem. generated from energy levels that typically involve the chemical
J. Vac. Sci. Technol. A 38(6) Nov/Dec 2020; doi: 10.1116/6.0000377 38, 061203-1
Published under license by AVS.
interactions between the atoms in chemical bonding (the molecular information that are critical for avoiding common mistakes in
orbitals).5 The spectral features of both the core and valence regions curve fitting. Important useful topics addressed include dealing
are sensitive to the chemical environments of the atoms in a sample. with overlapping peaks, fitting transition metal spectra, appropri-
In the core region, chemical shifts in the BEs yield a series of typi- ately constraining spin–orbit split peak ratios and energy separa-
cally overlapping peaks when the sample has atoms in different tion, and others.
chemical environments, e.g., oxidation states.6 The resulting data can
be analyzed by curve fitting. Curve/peak fitting is often the only way
to extract quantitative information from these spectra. II. BASIC APPROACH FOR FITTING XPS SPECTRA
The objective of curve-fitting high-resolution core XPS spectra A peak fitting model is defined in terms of component peaks
with a set of component peaks is to separate the photoemission and a background algorithm. The component peaks are specified
signal originating from distinct elemental or chemical states. using lineshapes, which are mathematical functions, and fitting
Parameters of importance extracted from curve fitting are the photo- parameters that permit a component peak to vary in a variety of
emission peak BE, full width at half maximum (FWHM), lineshapes, ways, including position, FWHM, area, Lorentzian character,
and area. The position of a component peak provides evidence for degree of asymmetry, and Gaussian character (The first four of
assigning it to an elemental or chemical environment. The FWHM these parameters will apply to all peaks, the latter two in some
and peak lineshapes are indicators of the chemical and physical envi- specific cases.) Sets of component peaks are summed (sum of all
ronment of the atom. Photoemission peak lineshapes can vary from component peaks) and then added to a background to form an
simple, narrow, symmetric shapes to complex structures characteris- approximation to the original data envelope.
tic of the different oxidation states of metals.5 Quantitative informa- The procedure of fitting component peaks to reproduce exper-
tion about the concentrations of the chemical states identified is imental photoemission spectra utilizes mathematical algorithms to
inferred by measuring the relative area of each component peak, the minimize a figure-of-merit as a measure of the closeness of the
calculation of which requires the separation of zero energy-loss mathematic model to the experimental data. The fitting algorithm
signals from the inelastically scattered background. The determina- incrementally alters the adjustable parameters, which leads from a
tion of accurate approximations to the background signal is also an current state to a termination state that represents a local minimum
integral part of the XPS peak fitting process. with respect to the figure-of-merit. The ability of the functions to
Curve fitting is sometimes misdescribed as being deconvolu- produce a reasonable fit from an initial guess in the iterative curve-
tion.4 Deconvolution is a different process to curve fitting. fitting process can vary. It is crucial to choose an initial guess that
Deconvolution is a process that attempts to remove the broadening is appropriate based on the physics and chemistry of the instru-
that results from instrumental factors, separating the “true” spec- ment and the sample. A poor set of initial guesses can cause the
trum from the observed spectrum. The process results in a new fitting algorithm to direct the fit into a local minimum that is not
spectrum with the data altered by the deconvolution process. representative of the sample physics and chemistry. That is, the
Deconvolution will not be discussed in this paper. curve-fitting process can give a mathematically good or even excel-
Our goal is to demonstrate useful, practical approaches for lent fit even though the component peaks in the final fit are not
analyzing XPS core regions (high-resolution or narrow scans) and chemically or physically reasonable.
what common mistakes should be avoided when curve fitting. A figure-of-merit, e.g., χ 2 or the standard deviation of the
Although there are several types of common errors in peak fitting, residuals, is a single number that is often used to guide adjustments
effective and useful approaches to peak fitting vary somewhat with to the numerous fitting parameters in the peak fitting process. The
the analysis objective, the type of sample, and the complexity of the fitting process may involve numerous paths though the parameter
spectrum. Fitting may be used to verify the composition of a pure space with the possibility of hitting and getting stuck in a number
sample (Sec. V), to separate overlapping peaks for quantitative analy- of local minima. It is, therefore, possible to obtain a range of out-
sis (Sec. VI B 1), to obtain the relative amounts of each phase from a comes depending on the starting point of the fit. There are a
sample with multiple phases of the same element (Sec. VI B 2), and number of additional checks that can be used to ensure that the
to examine in great detail the chemical spectrum for an element or physicochemical quality of a peak fit is adequate and that the current
phase for comparison with theory. This guide describes multiple fit is not just the best mathematical solution. These include the mon-
complications that can appear with fitting the core region, including itoring of the quality of the data reproduction with respect to the
multiplet splitting, conduction band interactions, and the use of noise; the applicability of the curve-fitting model to data of similar
achromatic X-radiation. origin; the generation of accurate peak areas for spin–orbit compo-
The following sections of the paper highlight important topics nents; and the accuracy of peak ratios for peaks from different ele-
for consideration during peak fitting. Section II describes a funda- ments or oxidation states of an element in a known chemical moiety.
mental approach to peak fitting, while Sec. III describes typical Optimization algorithms mathematically fit peaks to data. They
peak fitting errors observed in the literature and offers recommen- lack significant input from physics and chemistry, so optimization
dations to avoid them. Section IV addresses issues to think about based on a single value figure-of-merit may not yield comprehensive,
before starting to curve fit spectra (instrument setup, adequate data scientifically meaningful results. Physical and chemical information
collection, charge correction, lineshapes, and phenomena impacting can be added to a peak model through the selection of the line-
lineshapes and widths). Section V shows the fitting of poly(ethylene shapes, the number of component peaks within a peak model, and
terephthalate) (PET) as an example of fitting a reference spectrum the parameter constraints, all of which present a means by which
from pure material. Section VI summarizes a variety of tools and known relationships are imposed on otherwise independent
TABLE I. Table of commonly observed errors in XPS peak fitting.
Error Details How to avoid Reference

Labeling noise as chemical A “sophisticated” analysis does not fix Detection limits and Section IV B
components or presenting, data with a poor signal to noise ratio signal-to-noise should be
fitting, and/or interpreting sufficient to define component
data that is far too noisy to structures within spectra.
contain meaningful chemical Estimate the acquisition time
information per data-bin needed to achieve
signal-to-noise required for a
scientifically meaningful
analysis by peak fitting
Fitting spectral data with a A “sophisticated” analysis does not fix Data should have sufficient All examples herein
poor energy resolution data with a poor energy resolution energy resolution to permit
meaningful separation of a
signal by mathematically fitting
of components to data
Truncating the peaks in a Data are taken over a window that is Define energy acquisition All examples herein
narrow scan too narrow, which makes it difficult to regions of sufficient width to
fit an appropriate background and include surrounding noise and
component peaks. This includes only the leveled-off background.
utilizing one of the spin–orbit Include all components of
components in a fit spin–orbit splitting and
satellite peaks, unless the shift
is too large for a reasonable
narrow scan, e.g., the Co 2p
signals have a shift of 15 eV,
which would fit in a typical
narrow scan
Neglecting to include a This can change the area under the The inelastic background is an Section IV G and Background
background or using an curve and, therefore, the ratios of the integral part of a peak model. correction guide8
inappropriate background for fit component peaks Background selection should
the fit be based on the physical
properties of the materials
analyzed and should be
justified
Failing to make the This can change the area under the The background needs to Section IV G and Background
background match the curve and, therefore, the ratios of the connect a spectrum with the correction guide8
surrounding noise/spectrum fit component peaks noise level surrounding it,
using an average to find the
middle of the noise. In some
cases, the background may fall
slightly below the noise on one
or both sides of the peak
Having widely varying peak This mistake often results from Understand contributions of Section IV E
widths in a fit without neglecting to restrain the FWHM experimental and fundamental
chemical reason values of the fit components. This parameters into the FWHM,
error can drastically change component refer to the literature to
percentages determine appropriate FWHM,
determine FWHM values
experimentally, and use
constraints to keep FWHM
values within a small range,
two rules of thumb are ±10%
of FWHM and ±0.1 eV
TABLE I. (Continued.)

Mistreating spin–orbit This mistake involves disregarding Area and position constraints Section VI C
splitting or neglecting spin– spin–orbit splitting, neglecting to use for doublet peaks are well
orbit splitting the proper intensity ratio for a pair of defined and should be used
spin–orbit split peaks, and/or only when constructing peak
considering spin–orbit splitting for a models that include doublet
fraction of the fit components that pairs. Use reference databases
need it in a peak envelope. In many for understanding expected
cases, spin–orbit peaks are incorrectly spin–orbit properties such as
labeled as separate chemical states energy splitting, intensity
ratios, and FWHM differences.
Use constraints to define the
properties of the synthetic
peaks
Adding too many synthetic More peaks will generally “improve” a Only assign core level shifts to Section VI
component peaks to a fit fit, but they may not have chemical possible chemical and physical
meaning or statistical validity. The contributions. Use
lower limit for a plausible FWHM is complementary data from
determined by the energy resolution other analytical techniques to
for an instrument understand the different
chemistries possible.
Determine the energy
resolution for the operating
mode used to acquire spectra.
Use databases for accepted
chemically meaningful curve
fits of reference materials. The
number of components used to
model a given data envelope
should be consistent with data
collected from related
photoemission lines from the
same sample measured at the
same time (i.e., C—O peak
should be confirmed by both
C 1s and O 1s spectra)
Failing to include the original This mistake makes it impossible to The original, unsmoothed data All examples herein
data, only showing smoothed evaluate the quality of the original data should be shown. The
data, or only showing or the fit to it individual synthetic
component peaks and component peaks, the sum of
perhaps their sum as the the synthetic components, and
original spectrum the residuals should also be
shown
Using incorrect lineshapes— Choice of lineshapes affects the The choice of the lineshape Section IV D
ignoring asymmetry and relationship between components and depends on the type of
variability of Lorentzian/ relative areas of component peaks material being analyzed. The
Gaussian character selection of lineshape is a form
of constraint placed on
components in a peak model
Not showing the residuals to Excluding this information makes it The reported/plotted data All examples herein
the fit, and/or a difficult to determine the quality of the should include the residuals to
figure-of-merit for the fit the fit. It is also helpful to
goodness of the fit provide a figure-of-merit for
the goodness of fit, especially
TABLE I. (Continued.)

when multiple spectra are
shown/compared
Mislabeling or not Some examples of mistakes here Use reference databases that Sections VI A and VI B
considering the relevant include (1) shake-up (satellite) peaks describe all spectral features
physics and chemistry of the identified as chemical states in sp2 for reference materials.
spectra when identifying carbon, e.g., in nanotube or Measure data from standard
peaks graphene-based materials, (2) synthetic samples to verify the
peaks corresponding to metals or performance of an instrument
materials with sp2 carbon represented and understand the limitations
as symmetric when asymmetry would of XPS when analyzing similar
be appropriate, and (3) ignoring other materials of known
information from the XPS analysis, e.g., composition. Where
including peaks for oxidized carbon appropriate, use the data
when no oxygen is present in a acquisition parameters in the
material references/database
They are mislabeling higher This sometimes occurs in C 1s peak Use reference databases that Sections VI A and VI B
oxidation states incorrectly as labeling, where labels for the C—O and describe all spectral features
coming from lower oxidation CvO fit components may be reversed, for reference materials.
states or a carboxyl signal may be mislabeled Measure data from standard
as a carbonyl samples to verify the
performance of an instrument
and understand the limitations
of XPS when analyzing similar
materials of known
composition. Where
appropriate, use the data
acquisition parameters in the
references/database
component peaks. That is, the likelihood of achieving a chemically peak fitting that include appropriate considerations of the physical
reasonable fit is increased if the initial guesses are based on solid sci- and chemical nature of the relevant spectra. Some of the errors
entific principles. listed below are superficial and do not impact the conclusions of a
The art of fitting data with peaks is in selecting the appropri- paper. However, some fundamentally alter the interpretation of the
ate number of component peaks, making use of appropriate line- data and the conclusions drawn from it. Table I lists the errors in
shapes, and limiting the set of fitting parameters through XPS peak fitting that we have observed in the scientific literature
parameter relationships to produce peak models capable of measur- and suggests ways to avoid them. A more detailed discussion of the
ing physically meaningful quantities from XPS spectral forms. The errors can be found in a report.7
challenging part arises in selecting the correct physical solution
from the set of potential mathematical solutions. In practice, this is IV. XPS MEASUREMENT
best done by obtaining verification of the fitting model by repeating
these measurements on equivalent samples to confirm that the The chemical information that can be determined from curve-
observed changes are representative of the samples. Data collected fitting XPS spectra can only be physically meaningful if the data
should include measuring data from standard samples to verify the are appropriately collected, and proper consideration is made of all
performance of an instrument and understand the limitations of the physical and chemical contributions to the photoelectron
XPS when analyzing similar materials of known composition. spectra.
III. COMMON MISTAKES IN XPS PEAK FITTING A. Instrument calibration and performance
Following the principles outlined in this guide should help the Energy calibration of the instrument is a prerequisite for accu-
analyst avoid many of the errors listed below. Nevertheless, these rate peak energy identification. Any instability within an instru-
errors are regularly seen in the scientific literature.3 Of course, ment has the potential to alter lineshapes and accurate kinetic
there are many examples in papers of proper XPS analysis and energy registration. Regular instrumental calibration and check-up
are critical to ensure that the instrument is performing within the common error.3 Another possible error is to acquire data that have
acceptable limits of reproducibility and accuracy9 needed for physi- a poor signal-to-noise (S/N) ratio and to smooth it before curve
cally meaningful interpretation of curve fit results of spectra. fitting. (Note that the S/N ratio varies across an XPS survey spec-
Figure 1 shows two Nb 3d photoemission spectra collected trum.3) Smoothing may introduce changes in the spectral shape
from a sample that was mainly metallic with a small amount of and width;14,15 changing the underlying physics, and may lead to
NbO and NbO2 present on the surface. The bottom spectrum dis- erroneous interpretation of curve fitted spectra.
played an incorrect (compressed) spin–orbit splitting for the metal-
lic component and a second component that did not correspond to C. Accurate charge correction
one of the expected oxide components. These problems were iden-
tified by comparison with Nb spectra published in the literature Accurate BE identification relies not only on the instrumental
(previously collected data and resources described in Sec. VI A) energy scale calibration but also on the accuracy of charge correc-
and were due to a malfunctioning pass energy (PE) control board. tion if charge compensation is employed during data acquisition.
The correct spectrum in Fig. 1 (top) has all three expected compo- Charge compensation is often required when measuring XPS
nents (Nb, NbO, and NbO2). spectra from insulating materials. A charge builds up near the
Even though modern XPS instruments are becoming more surface of these materials as the photoelectrons are emitted. This
stable and reliable, it is crucial to perform regular energy scale and usually shifts the photoelectron energy and distorts peak shape. For
linearity calibrations as prescribed by the standards.11,12 Recently, a details on charge compensation, please refer to the XPS Guide:
procedure that allows the performance and calibration of an XPS Charge compensation and BE referencing for insulating samples.16
instrument to be checked rapidly and frequently was published.13
D. Lineshape of an XPS peak
One of the most influential aspects of a successful peak model
B. Adequate data acquisition is the lineshapes or the shapes/functions appropriate for modeling
The quality of information extracted from curve-fitting XPS the photoemission process after measurement by an XPS instru-
spectra can only be as high as the quality of the experimental data. ment. These lineshapes must accurately represent, or at least closely
The spectra acquired are not always of sufficient intensity and reso- approximate, the signal measured by an instrument. Therefore, it is
lution to perform useful peak fitting. Instrumental contributions to essential to understand the role of the instrumentation in modify-
the spectrally resolvable chemistries are discussed below. The ing peaks.
analyst should also consider the signal-to-noise of the spectra pro- The XPS process is relatively simple.17 X-ray light in the
duced. For elements with low sensitivities and/or that are present intrinsic process causes an electron to move from an initial, occu-
in low concentrations, overinterpretation of noise as chemistry is a pied energy level to a final, virtual energy level that has energy
FIG. 1. Nb 3d spectrum collected using a PHI 5600XPS system (Ref. 10). The bottom spectrum was collected with a malfunctioning PE board. The top spectrum was col-
lected after the PE board had been replaced. A Shirley background was used.
greater than the Fermi level of the solid under study. The electron as additional intrinsic, processes can occur after the intrinsic XPS
is then lost from the virtual final state energy level and escapes process that can give additional spectral features.
from the solid at a specific energy. This energy is subsequently In choosing a Gaussian–Lorentzian mix, it is important to
measured in the spectrometer. The uncertainty principle gives the note the following points:
initial energy level a Lorentzian energy distribution (discussed in
Sec. IV E). The basic shape of the XPS peak recorded in a spec- • Typically, it is found that compounds have a more Gaussian
peak shape than metals, which usually have considerable
trometer is modified by instrumental and other factors (such as
Lorentzian character. One reason for this is the presence of
phonon broadening) to give a Gaussian contribution.18 This leads
to a measured lineshape that is a convolution of a Gaussian and a optical phonons in compounds, whereas metal has principally
Lorentzian function. This function, known as the Voigt function,19 low-energy acoustic phonons leading to an increase in vibrational
most accurately reflects the nature of this intrinsic XPS process. broadening in compounds and thus more Gaussian character.
This topic is discussed in Sec. IV E.
XPS peaks can be expressed by Voigt functions that vary in
• In the curve-fitting process, the analyst starts the process by sug-
their amounts of Gaussian and Lorentzian character. This can be
done by identifying a Gaussian (ghm) and a Lorentzian (lhm) gesting possible values for the various peak parameters such as
FWHM. BE, FWHM, Gaussian/Lorentzian character, and peak heights. It
A parameter called the “Gaussian/Lorentzian mix,” glmix, may is usually necessary to fix some of these parameters in order for
the iterative process to converge. The analyst will determine
be defined as
typical values for Gaussian–Lorentzian mix for their instrument,
but typical values for many instruments are given below:
lhm o Compounds: glmix below 10% for Voigt functions and M = 0.5
glmix ¼ ,
lhm þ ghm for pseudo-Voigt product functions and M = 0.2 for
pseudo-Voigt sum functions.
o Metals and elements: glmix above 60% for Voigt functions and
which takes the value 0.0 for a pure Gaussian and 1.0 for a pure
M above 0.8 for pseudo-Voigt functions and M above 0.6 for
Lorentzian. Thus, the Voigt function varies the amount of
pseudo-Voigt sum functions.
Gaussian and Lorentzian character by using Gaussian and
Lorentzian FWHM values that are usually different. Figure 2 shows These represent good starting guesses for the Gaussian–Lorentzian
a plot of the Voigt function with glmix = 0–0.9999. It should be mix values.
noted that Gaussian–Lorentzian sum and product functions, which
approximate the Voigt function, called pseudo-Voigt, have also E. FWHM of the XPS peak
been widely used in XPS peak fitting.20 In these pseudo-Voigt func-
tions, there is a mixing ratio (M), which controls the amount of The FWHMs of the Voigt function peaks used in core XPS
Gaussian and Lorentzian character, typically M = 1.0 for a pure peak analysis depend on several factors discussed below.
Lorentzian and M = 0.0 for a pure Gaussian, but sometimes these
M values are reversed. As discussed in Sec. IV F, extrinsic, as well 1. Lifetime of the core hole—the natural linewidth
The photoelectron peak is broadened to give a Lorentzian
shape that depends on the lifetime of the core hole resulting from
the photoelectron process. The core hole corresponds to an excited
state, and various processes fill this hole, especially x-ray or Auger
emission. There are several tabulations (Refs. 22 and 23 and refer-
ences therein) of natural linewidths, a number of which are based
upon experimental data from x-ray emission spectroscopy and
Auger spectroscopy and calculations. Krause and Oliver pub-
lished23 a tabulation of core energy levels from atomic number 10
to 110, and many other papers report natural linewidth values,
including those using XPS data.22
2. Linewidth of the x rays used to eject the

photoelectron
The natural linewidth of core energy levels increases as the
binding energy, BE, of the core energy level increases. Thus, the
FIG. 2. Plot of Voigt functions that can be used to describe the shape of XPS linewidth of the Kα1,2 x-ray emission lines increases as the atomic
peaks. The functions are calculated for a single peak with an FWHM of 400 number (Z) of the x-ray target increases (by a factor of Z4) for the
channels and a peak maximum of 10 000 counts over a range of 4001 chan- K lines.24 For example, aluminum Kα x rays have a much narrower
nels, 2000 channels to the right and left of the peak. When these parameters linewidth than higher energy chromium Kα x rays. Higher energy
take a value of 0, the peak is a pure Gaussian. When they take a value of 1,
the peak is a pure Lorentzian (Ref. 21).
x-ray sources are used in hard x-ray photoelectron spectroscopy,
abbreviated as HX-PES or HAXPES. Photoelectrons from deeper
core levels can be excited by higher energy x rays compared to soft consistent with a balance between the appropriate signal to noise
Al Kα x rays. For example, for Al, a soft x ray can excite up to the ratio and analysis time available, used to get the best data for curve
2s orbital only, but a hard x ray can excite up to the 1s orbital. fitting.
Figure 3 shows the Al 2p and Al 1s core regions obtained
using a Cr x-ray source, which has an energy of 5414.7 eV. The
kinetic energy of Al 2p photoelectron is ∼5336.8 eV, which is much 4. Resolution of the spectrometer used to measure the
higher than the kinetic energy of Al 1s electron (∼3850.3 eV). The photoelectron energy
spectra in Fig. 3 are overlayed to the same maximum and intensity Most XPS instruments use hemispherical analyzers. Usually,
for comparison. In Fig. 3(a), the Al 2p curve fitted with two asym- the photoelectrons have their energy adjusted in a lens system so
metric spin–orbit components separated by 0.44 eV and at 2:1 that they enter the hemispherical analyzer with particular kinetic
intensity ratio. The causes and treatment of asymmetry are dis- energy called the PE. The analyzer settings, including PE, contrib-
cussed in Sec. VI F. In Fig. 3(b), Al 1s and Al 2p3/2 components of ute to the resolution function of the instrument and hence to the
Al 2p transition are overlayed to the same maximum and intensity energy resolution and photoemission peak shape. Therefore, it is
for comparison. The FWHM of Al 1s spectrum is 1.35 eV while important to determine the energy resolution for the operating
that of Al 2p3/2 component is 1.08 eV, demonstrating the increase mode used to acquire spectra that will be curve fitted.
of lifetime broadening for the deeper core level.
5. Chemical environment of the atom from which the
3. Effect of the spectrometer used to measure the pho- core photoelectron was ejected
toelectron energy on the linewidth The chemical environment of the atom from which the core
The spectrometer that measures the kinetic energy of the pho- photoelectron was ejected has a substantial effect on the FWHM.4
toelectrons adds additional width to the natural linewidth, as well In particular, the intrinsic photoelectron process couples with
as giving Gaussian character to the peak lineshape. This means that phonons in the solid, resulting in broadening of the core peak and
the observed linewidth is generally substantially different from the giving the peak Gaussian character. Metal phonons are often domi-
natural linewidth necessitating the use of the Voigt function nated by acoustic phonons of low energy, whereas metal com-
described above. Tables of natural linewidth (e.g., Ref. 22) can be pounds such as oxides and carbonates have extensive optical
helpful in setting the Lorentzian component of the Voigt function phonons of much higher energy resulting from multiple solid-state
in a curve fit of a spectrum but rarely describe the measured peaks vibrational modes.25 Thus, metals normally have substantially nar-
themselves. Typically, the analyst should obtain the spectrum with rower FWHM values than metal compounds and more Lorentzian
the best resolution available from the specific spectrometer, character. Figure 17 in Sec. VI F for the Al 2p region illustrates this
FIG. 3. Core XPS spectra of aluminum metal obtained using Cr Kα photon energy of 5414.7 eV. Spectra obtained using PHI Quantes instrument. (a) Al 1s and Al 2p
spectra overlayed to the same maximum and intensity for comparison. The Al 2p curve fitted with two spin–orbit components separated by 0.44 eV and at 2:1 ratio; (b) Al
1s and Al 2p3/2 component of Al 2p transitions overlayed to the same maximum and intensity for comparison. A Shirley background was used.
—it can be seen that the oxide peak has a substantially greater approaches for background inclusion, and a forthcoming paper8 is
FWHM than the metal peak when measured at high resolution. devoted to this topic. There are three major approaches:
• The removal of the background to yield a spectrum with an
F. Existence of extrinsic processes as well as additional approximately horizontal background. This approach alters the
intrinsic processes experimental data with the subsequent curve fitting being made
The photoelectron process can be simplified into a three-step on the altered data. This can lead to errors depending upon the
model:26 chosen background model. It also deprives the viewer of the
ability to compare the original experimental data with the curve
• Step 1: The excitation of the electron from the initial energy level fit. This approach is not recommended.
to the final virtual orbital state. Processes associated with this • The addition of a fixed background to background subtracted spec-
step are called intrinsic processes. trum before peak fitting, where this background is not subtracted
• Step 2: The transfer of the photoelectron to the surface. Processes from the spectrum, and it is shown in the final fit. This approach is
that occur after the first step are called extrinsic processes. mathematically identical to the previous one, but it allows the
• Step 3: The escape of the photoelectron from the surface into the viewer to see the original data, the background, and the fit together.
vacuum. • In the active approach, the background contains parameters that
The first two steps are sometimes called the two-step model. are included as potentially variable factors in the fit. This method
In addition to the key intrinsic process, there are intrinsic pro- also preserves the data in its original form but allows for different
cesses that involve the ejection of a photoelectron, as follows. backgrounds in different regions of the spectrum. In some insula-
tors and gases,30 e.g., in near ambient pressure XPS,31–34 the XPS
• Plasmons25 can give rise to additional peaks in a spectrum. Both background can be linear, but most XPS backgrounds in metals
bulk and surface plasmons are possible. For example, aluminum and semiconductors are nonlinear. The active approach allows for
metal has a rich plasmon structure.27 Plasmons can also be addressing these differences in complex materials.
extrinsic.
• Shake-up5 processes in which a valence electron and a core elec- We do caution the reader that a simple linear background between
tron are excited. If the valence electron is promoted to another the starting and ending points in a spectrum is incorrect and will
valence energy level in the sample, this is called a shake-up cause substantial errors in the peak fitting of spectra where the
process. If the valence electron is ejected as an additional photo- measured background is not flat. As discussed in the Practical
electron, the process is called a shake-off process. Guides for X-ray Photoelectron Spectroscopy: Quantitative XPS,35
• Multiplet splitting5 arises from samples that have unpaired elec- the line describing the background should, ideally, go through the
trons because there is more than one final state depending upon middle of the noise in the data before and after the peak.
the number of spin up and spin down electrons in these final
states. Transition metal compounds are often paramagnetic and, V. EXAMPLE CURVE FIT OF REFERENCE SPECTRA
in this case, display multiplet splitting in their core XPS data FROM PURE MATERIALS—PET
(discussed in Sec. VI C).
We fit here a reference spectrum taken at high resolution from
• High Binding Energy Assymetry28 Conduction Band interactions
an XPS database of organic polymers—PET.36 PET is an important
give a tail of approximately exponential shape to the core XPS of
reference polymer that is used for verifying instrument performance,
conducting materials (Sec. VI F).
including charge neutralization validation.4,13,37,38 Monochromated
Extrinsic processes include Al Kα x rays (1486.3 eV) were used to collect these data on a Scienta
ESCA300 spectrometer. The energy spread of the monochromator is
• Plasmons, which can also be intrinsic. predicted to be 0.26 eV. A PE of 150 eV was used, and high energy
• Inelastic processes often occur between ejected photoelectrons resolution was achieved by using an appropriate analyzer entrance
and other atoms and molecules. These processes cause loss of aperture width. The FWHM of the C 1s envelope was determined to
energy of the photoelectron and represent the principal contribu- be 0.67 eV. Low-energy electrons were used for charge compensation.
tion to the background in XPS.29 There are effective software The PET structure is shown in Fig. 4. Based on its chemical
models for the study of this loss structure, and these studies can formula (C10H8O4)n, there is 71 at. % of C and 29 at. % of O in
provide valuable information. These processes can have a large PET. There are 10 carbons in the repeating unit of the polymer, 4
effect on peak ratios as a function of emission angle. of which are present in the aromatic ring (labeled 1) with a BE of
284.7 eV. Two other carbons (labeled 2) in the aromatic ring are
secondary shifted carbons such as C*—C(vO)O, which will con-
G. Background subtraction tribute to the BE of ∼285.3 eV. Two carbons that are singly bonded
Most XPS spectra have a significant background, and account- to oxygen (labeled 3) have BE of 286.2 eV. The other two carbons
ing for the background contribution is an important aspect of the are in carboxyl (ester) groups (labeled 4), and their BE is 288.7 eV.
curve-fitting process. The choice of the type of background and Out of the four total oxygens, half are present in the OvC part of
selection of end points has the most significant impact on the area the carboxyl/ester group (labeled 1) at 531.6 eV, and the other half
under the curve, and hence the ratios of the individual peaks used to are in the O—C part of the carboxyl/ester group (labeled 2) at
curve fit the spectrum. There have been numerous studies devoted to 533.2 eV.
FIG. 4. High-resolution C 1s and O 1s spectra of PET fitted using symmetrical GLS (fixed M = 0.1) peaks. (a) and (b) Initial set of peaks added to initiate the curve fit. (c)
and (d) Final curve fitted spectra. Residuals are displayed below the spectra. A Shirley background was used.
The C 1s and O 1s spectra are accompanied by a survey scan Once the necessary component peaks have been added into the
confirming that no other elements are present at the PET surface. envelope, constraints on the adjustable parameters need to be estab-
When a Shirley background is used for quantification of the high- lished. If the goal is to understand the chemical state information in
resolution C 1s and O 1s spectra, 69 at. % C and 31 at. % O are the spectra, adding parameter constraints will improve the stability
detected. Slightly different concentrations due to the possible pres- of the peak model with respect to the noise. However, with each new
ence of adventitious carbon38 are observed. constraint, the output from the optimization converges ever more
Figure 4 shows C 1s and O 1s high-resolution spectra (narrow closely to the solution defined by these constraints until the useful-
scans) with component peaks added to initiate a curve fit. The orig- ness of fitting peaks to the data is lost. If the goal is to measure the
inal data from the “High Resolution XPS of Organic Polymers: The intensity changes for a series of samples from the same study and a
Scienta ESCA300 Database”36 have been fit using the commercial peak model is well formed, then a rigid peak model that is heavily
software MultiPak 9.9.39 Four component peaks are added to the constrained will tend to return more consistent intensities for data
carbon spectrum, reflecting the number of different chemical envi- with similar chemistry and experimental conditions. Somewhere
ronments that contribute to the resolvable BE shifts discussed near the middle of these two extremes is the domain for most photo-
above. Due to the aromatic structure of the benzene ring, a emission peak fitting.
shake-up signal is observed above 290 eV, which should represent FWHM constraints and the indirect constraints imposed by
ca. 7% of the total carbon signal based on the reference data.36 This lineshape selection are the two main parameters used in peak
shake-up contribution is fit with one or more peaks. fitting. Other types of constraints, such as spin–orbit intensity ratio
for spin–orbit splitting, are discussed in Sec. VI C. For spectra with and 58% from O2 (533.2 eV) (with shake-up peak at 538.5 eV and
well-defined peak resolution, e.g., the C 1s narrow scan of PET, the contamination peak at 535.0 eV excluded from the total area).
FWHM can be chosen based on the widths of the individual peaks Based on the area under each component peak, the quantifica-
to reproduce the experimental curve as best as possible. Some var- tion of PET can be derived, as shown in Table II. This direct, quan-
iation (ca. 10% of the FWHM or ±0.1 eV) might be justified among tifiable comparison of the carbon and oxygen in the polymer can
different peaks due to small secondary effects. As described above, be used to confirm both the structure of the polymer and that the
a function having both Gaussian and Lorentzian character often curve fit adequately reflects the chemical structure.
best describes the experimentally derived spectra. The
pseudo-Voigt function that is used to approximate the Voigt func-
tion is typically either a product function or a sum function. Both
functions involve the mixing of equal width Gaussian and VI. AVOIDING MISTAKES DURING PEAK FITTING
Lorentzian functions with a mixing ratio (M) defined in the analyt-
ical function. The mixing ratio, M, takes the value 0.0 for a pure A. General information and databases of reference
Gaussian and 1.0 for a pure Lorentzian, though some authors have spectra with information on peak widths, separations,
the reverse definition. During the iterative fit, a fixed GL mixing and satellite positions
ratio can be chosen, or a range of GL mixing ratios can be used There are several resources available to assist in curve fitting,
during optimization to find the best fit. In this example, a sum including complex spectra that contain several chemical compo-
function of Gaussian and Lorentzian (GLS) with M = 0.1 (where nents. The NIST XPS database40 and XPS Spectra (Chemical Shift/
M = 0.0 is for 100% Gaussian) was used. Binding Energy)41 are searchable databases containing line posi-
Similarly, based on the sample chemistry, two peaks to be fit tions, chemical shifts, values for doublet splitting, and energy sepa-
are added to the O 1s spectrum to best approximate the number rations of photoelectron and Auger-electron lines. X-ray
and type of chemical moieties present. That is, as predicted by the Photoelectron Spectroscopy (XPS) Reference Pages42 and the XPS
chemistry of PET, the O 1s spectrum is fit with two distinct peaks Reference Table of Elements43 contain curve-fitting details, BEs,
of approximately equal height and similar FWHM. Due to the aro- FWHMs, spin–orbit splitting values, references, and other practical
matic structure of the benzene ring, some shake-up signature is notes for most of the elements in the periodic table. The XPS sim-
observed above 539 eV. One more peak is added at ca. 535 eV to plified website also contains useful information for narrow scan
account for surface contamination. analysis.44
During an iterative fit, constraints of FWHM and lineshapes There are various valuable databases that contain high-quality
are used to minimize the residuals—the difference between experi- spectra of known materials that can be downloaded. These include:
mental and fitted curves. It is good practice to show the residuals
of a fit. Figure 4 and Table II show the final parameters used to fit • Representative spectra for each element in a book published by
the spectra. The percent area obtained is slightly different from the Physical Electronics and used by analysts for many years.10
data published in the Handbook due to the different lineshapes • The journal Surface Science Spectra (SSS). This journal has an
used in the original Handbook.36 The resulting peak model consists invaluable collection of spectral data with full experimental
of the peak position and percent area that each component peak details. From volume 15 onwards, data can be downloaded as a
occupies out of the total carbon signal. The component peak posi- text file. SSS contains many examples of peak fitting.
tion information is then translated into the chemical state of the • eSpectra®45 is a database and comparative tool that contains the
sample. Curve fitting of the C 1s spectra results in 40.3% of the complete collection of the spectra published in Surface Science
area coming from C1 (284.8 eV), 20.2% from C2 (285.3 eV), 20.2% Spectra as well as from other sources.
from C3 (286.3 eV), and 19.3% from C4 (288.7 eV) (with shake-up • The XPSSurfA database hosted by La Trobe University in
peak at 291.3 eV excluded from the total area). Curve fitting of the Australia contains spectra from high-quality samples that were
O 1s spectra results in 42% of the area coming from O1 (531.7 eV) collected under precise conditions.46
TABLE II. Parameters used to curve fit C 1s and O 1s from PET in Fig. 4.
C 1s
BE, eV 284.8 285.3 286.3 288.7 291.3
FWHM, eV 0.9 1.0 1.2 0.9 2.5
% Area 39.4 19.7 19.7 18.9 2.3
% Area without a shake-up 40.3 20.2 20.2 19.3 0.0
O 1s
BE, eV 531.7 533.2 535.0 538.5
FWHM, eV 1.1 1.4 1.4 2.0
% Area 39.6 55.9 2.0 2.8
B. Use of reference spectra as to why peak assignments are difficult with transition metals. The
first is the combinations of intrinsic and extrinsic processes, such as
1. Resolving overlapping peaks
multiplet, shake-up, and plasmon loss structures, contributing to the
In this example, the N 1s spectrum of N-doped HfO2 overlaps overall photoelectron shape of the pure metals and their different
with the Hf 4p3/2 region. The Hf 4p3/2 peaks appear between 375 coordination states. The second is the overlap of the various chemi-
and 390 eV, while some higher BE components contribute to the cal states usually present in transition metal-based systems. The third
energy range where a signal from N 1s is expected. To solve this is that exposing transient metal compounds to air always results in
problem of overlapping spectra, it is important to acquire the oxidation and formation of both stochiometric and substochiometric
spectra from the reference material, a thick Hf oxide film without oxidation states. Another complication is that these oxides can
nitrogen doping in this case. Figure 5 shows a high-resolution Hf have varying degrees of conductivity, which may affect the position
4p3/2 region in which several peaks are included to fit the experi- and shape of photoelectron peaks due to charging. Early and
mental data. even current databases, such as NIST and Handbook of X-ray
The Hf 4p3/2 region [Fig. 5(a)] has features that occur in the Photoelectron Spectroscopy,10 usually indicate that there are multiple
same region where N 1s signal is present. In this example, the chemical states that can correspond to the same BE and, at the same
purpose of curve-fitting Hf 4p3/2 spectrum is not to extract the time, they provide single BE for a unique chemical environment of
chemistry of Hf but rather to create a mathematically rigid model the transition metal. However, as multiple reports of reference com-
in which peaks overlapping with the N 1s region are constrained in pounds have shown,47–49 complex spectral structure, which is the
position, width, and area to the higher intensity peak in the lower result of an envelope of multiplet peaks and/or other intrinsic and
BE region which is free of overlap with the N 1s region. Two peaks extrinsic effects, is often present with the different chemical states of
due to Hf 4p3/2 in the region where N 1s is located, i.e., between the element. Simply put, the multiple chemical states of a single tran-
390 and 405 eV, are constrained in intensity, position, and width sition element often give radically different spectra.
with respect to the most intense peak at 383 eV. For an N-doped Figures 6(a)–6(c) show spectral signatures for pure metallic
material with two different loadings, the rigid set of peaks is intro- Ni, NiO, and Ni(OH)2, as reported by Biesinger et al.47 The com-
duced into the high-resolution N 1s/Hf 4p3/2 region [Figs. 5(b) plexity of the spectral signatures due to contributions of the multi-
and 5(c)]. The intensity of peaks overlapping with N is controlled ple processes that can occur when the photoelectron escapes the 2p
by the height of the most intense peak, and this leads to a poor fit. orbital is obvious. Therefore, the most accurate approach to solve
This fit, though, is consistent with the Hf, so additional peaks must this problem is to use a curve-fitting parameter either developed by
be added to complete a curve fit. These peaks are the contribution the analysis from pure reference spectra, if they are available, or, to
from N 1s photoelectrons. This approach is successful even in sit- use curve-fitting parameters from reference compounds published
uations when N loading into the sample is very low, assuming that in the literature. The first approach is preferred as it ensures that
the data have been acquired with an appropriate signal to noise. the same spectral and analyzer conditions are used to collect the
data from the samples and reference materials. We emphasize that
the series of peaks used to fit the narrow scans in Figs. 6(a)–6(c)
2. Fitting transition metal spectra based on reference are simply employed to fit the peak envelope to create an overall
spectral envelopes shape that will be used in subsequent peak fitting, more than they
High-resolution spectra of transition metals are among the are intended to have specific chemical meaning.
most challenging spectra to peak fit.47–49 Indeed, it is common to Figure 6(d) overlays the photopeak shapes (or envelopes) that
see peak fitting of transition metals that oversimplify assignments were created by Biesinger et al. based on fitting the narrow scans in
of peaks to individual chemistries and subsequently have erroneous Figs. 6(a)–6(c) for Ni, NiO, and Ni(OH)2.47 The ambiguity of
interpretations of the results. There are several contributing factors finding a unique spectral signature for pure reference material is
FIG. 5. High-resolution region of Hf 4p3/2-N 1s electrons for (a) pure HfO2, (b) highly doped N-HfO2, and (c) low-doped N-HfO2. The peak model in (a) is a mathematically
rigid constrained model used in separating contribution from the Hf 4p3/2 region and N 1s electrons in (b) and (c). A Shirley background was used.
obvious. However, through a linear combination of the photoelec- input from other spectral features exists. In this case, care should
tron signatures representing the pure chemical states, curve fitting be taken in deciding physical constraints to be used during the
of the mixed chemical states of the transition metals is possible. optimization of curve fit parameters.
This is essentially a classical least squares (matrix algebra) problem For most elements, participation in chemical bonding with
in which one has the spectrum of the mixture of compounds as other elements causes an increase in BE, especially when the ele-
well as those of the pure components.50 Figure 6(e) shows a curve ments to which they are bonded are more electronegative. That is,
fit of the spectrum from a mixed Ni-Mo oxide, which has had the for elements having multiple possible oxidation states, more oxi-
background removed, using this type of complex photopeak model. dized chemistries will usually show higher BEs. This pattern is well
The relative ratio of the various chemical states of Ni can be established for carbon, where an increased number of oxygen
extracted from this information, assuming that one knows informa- atoms bonded to a carbon atom leads to a steady increase in its
tion on the physical form of the material (powder, spheres, layered BE.6 Here, the presence of more electronegative oxygen atoms
surface structure, etc.) supporting the chemical composition deshields the carbon atom, effectively increasing the nuclear charge
derived by XPS fitting. felt by its electrons, which raises their BEs (and lowers their kinetic
energies in XPS). In many cases, the least oxidized (lowest BE)
form of an element will produce the “cleanest” peaks in an XPS
3. Finding appropriate FWHM values for unknown spectrum that can then be used to select the best FWHM value for
samples when no references are available the fit. However, this will not always be so—it will depend on the
In certain situations, an analyst is confronted with the need to sample chemistry.
curve fit spectra from complex multicomponent materials where Figure 7 shows a high-resolution C 1s spectrum in which the
finding appropriate references may not be possible and limited highest intensity component results from the contribution of
FIG. 6. (a)–(c) High-resolution Ni 2p region for pure reference compounds curve fitted based on Biesinger et al. (Ref. 45) peak models; (d) pure reference spectra over-
layed; (e) Ni 2p for Ni-Mo oxides fitted using developed peak models. A Shirley background was used.
FIG. 7. High-resolution C 1s spectrum of PET fitted using peaks with three different widths to match the right-most slope of the spectrum. Grey—experimental line, green
(dark gray)—peak. The upper insets show zoomed-in areas between 282 and 284.5 eV. The linear background was used.
carbon in the lowest oxidation state in the material, which is also The separation between the 3/2 and 1/2 components of the S 2p
the most abundant. In Fig. 7(a), the FWHM of the component orbitals is fixed to 1.16 eV, and so is the area ratio to 1:2.
peak is too narrow, which results in part of the spectral area being It is worth noting that in the case of p, d, and f levels, spin–
under fitted. In Fig. 7(c), the FWHM value is too broad, which orbit splitting occurs, and in a number of cases, the FWHM value
results in overfitting the right shoulder of the spectrum. The best of the higher BE component is greater than the lower BE compo-
match between the component peak and the experimental data is nent, an effect which has been described as a Super Coster–Kronig
shown in Fig. 7(b). The FWHM value obtained from this match is effect.52 When the FWHM of spin–orbit split components differs,
probably an adequate representation of the physical, chemical, and it is essential that the curve-fitting program has the capability of
instrumental contributions to the data. To a good first approxima-
tion, this FWHM could be used for other component peaks that
might be considered in the fit. Nevertheless, the lone peak at ca.
289 eV in this spectrum is another reasonable choice for determin-
ing the FWHM values of the fit components—it seems to have far
less overlap with other signals than the larger peak around
284.5 eV. It would be advisable to consider both FWHM values in
this curve fitting (they should be quite similar). Further analysis
would be needed to determine which would be most appropriate,
or their average, range of values near the average, etc.
C. Spin–orbit splitting ratio and energy separation

Area parameter constraints are particularly useful for spin–
orbit peaks, which are doublet peaks originating from the same
electron configuration initial state where the final state electronic
configuration is split between two possible outcomes. Physics for
the photoionization of electrons dictates these double peaks appear
offset in energy, representing the difference in energy between the
final states and at a defined ratio in terms of peak area (inset,
Fig. 8). Scofield cross sections51 were calculated for photons with
energies corresponding to Al and Mg x-ray gun anodes, and these
cross sections include relative intensity values for both peaks in a
doublet pair. Thus, the ratio for these peaks can be readily fixed by
making use of Scofield cross sections to estimate the relative area
FIG. 8. High-resolution S 2p spectrum fitted with two doublets separated by
imposed by area constraints within a peak model. Figure 8 shows
1.16 eV and area ratioed to 1:2 to each other. A Shirley background was used.
the S 2p spectrum that was fitted with two sets of doublet peaks.
TABLE III. Spin–orbit splitting for common transitions.
Metal Oxide
Ti 2p 6.1 5.7
Si 2p 0.63 N/A
Fe 2p 13.1
In 3d 7.6
Mo 3d 3.15
Ag 3d 6.0
Au 4f 3.7
Hf 4f 1.68–1.71
Pt 4f 3.35
setting the FWHM of the spin–orbit components to an adjustable

ratio while keeping the peak areas in the expected area ratio.
Table III shows energy separation for a few common transi-
tions. For some transitions, such as Ti 2p and Si 2p, there may be a
difference in separation for different chemical states. For example,
spin–orbit energy separation is smaller for Ti oxide than for metal,
while spin–orbit splitting is only used in fitting metallic Si and not
higher oxidation states. The separation may be smaller than energy
resolution or as large as 20 eV.
For elements like the transition metals with a rich range of
oxidation states, e.g., Mo, there may be challenges using a single
doublet for each chemical state. Photoemission from Mo4+ is an FIG. 9. Crystalline molybdenum dioxide (Mo4+) with contamination from Mo6+.
example of where the relationship between the chemical state and a The peak model involving these three sets of doublet components includes an
example of an active approach to modeling background signal. The component
pair of synthetic components representing a doublet is not appro-
shapes used to the model background are exponential decay curves convoluted
priate. Following Scanlon et al.,53 Mo4+ is represented by two dou- with a Lorentzian.
blets, while Mo6+ is modeled using a single doublet (Fig. 9). It is
also an example of where complex data envelopes for a specific oxi-
dation state are essential for correlating the amount of substance
with intensity derived from synthetic components. That is, the the measured relative area for components in a peak model, and
amount of material calculated for Mo4+ requires the summation of therefore how the signal is allocated to a chemical state. The choice
the signal corresponding to four synthetic components labeled [1] of background also influences the computed areas of the compo-
Mo 3d4+ and [2] Mo 3d4+. nents. A regularly encountered example that illustrates these factors
In some cases of spectral overlap between two different transi- is that of a silicon oxide film on elemental silicon. The Si 2s and Si
tions, the spin–orbit splitting ratio and separation constraints can 2p signals are a useful example because both photoemission lines
help resolve overlapping peaks. Figure 10 shows a region in which exhibit features that can be identified as silicon oxide and elemental
both Sb 3d and O 1s contribute. That is, the signal from the silicon. They are relatively close in BE and therefore show similar
oxygen photoelectrons overlaps with a larger Sb3d5/2 component, instrumental responses, but they are different in terms of component
while the smaller Sb 3d3/2 component is free of overlap. In this FWHM and lineshapes. Notably, the Si 2s signal measured on
case, peaks included in the 3d3/2 region can be a constraint in posi- modern instruments with monochromatic x-ray sources shows char-
tion and intensity to the peaks contributing to the 3d5/2 region. acteristic lineshapes with wings typically associated with a Lorentzian
Figure 10(a) shows two doublets from the metallic and oxide forms shape. One way to allow for extended wings in spectral features is to
of Sb constrained rigidly between each other. The intensity of the fit basic background curves as part of the optimization step. The Si
two peaks in the 5/2 part of the spectrum is limited by the intensity 2s data in Fig. 11 are fitted using Voigt lineshapes representing ele-
of the two peaks in the 3/2 part. A large deviation in the residuals mental and oxide signal plus two lineshapes with background char-
points to where a peak corresponding to O 1s photoelectrons acteristics. A component in the peak model is used to emulate a
should be included. When the peak due to O 1s photoemission is Shirley response to model inelastic scattering due to elemental
included [Fig. 10(b)], the contributions of overlapping transitions silicon. At the same time, an offset summed with the Shirley back-
can be determined quantitatively. ground is defined by making use of a top-hat lineshape of width
greater than the energy interval shown in Fig. 11 that is adjusted to
allow the use of Voigt lineshapes when the fitting is performed.
D. Choosing a correct lineshape and background In the case of the silicon dioxide overlayer on silicon, the Si 2p
When selecting lineshapes for use in modeling spectra, one and Si 2s core level measurements should return equivalent cor-
should be aware that the choice of lineshapes has an influence on rected areas for component peaks. An equivalent model for Si 2p
FIG. 11. Si 2s measured using a PHI Quantum 2000 monochromatic Al x-ray

source with pass energy 46.95 eV from a sample consisting of a 4 nm thick
silicon oxide layer over a substrate of elemental silicon. A horizontal background
is offset from the data (green zone, lowest intensity section). Two curves (bright
red) fitted during optimization representing background signal in addition to the
green zone are defined as a Shirley background generated by the elemental
FIG. 10. O 1s/Sb 3d region. (a) Two doublets used to fit Sb 3d contributions by silicon component (blue, lowest BE peak) and a top-hat lineshape, the height of
constraining the intensity, position, and width of the peaks in the 5/2 region with which allows lineshapes of significant Lorentzian character to be used to model
respect to those in the 3/2 part. A high negative residual in the range of 530 eV both elemental Si 2s and oxide Si 2s intensity.
is seen; (b) a peak due to O 1s electrons (dashed) must be included to accu-
rately complete the curve fit. A Shirley background was used.
comprised of core photoelectron peak, shake-up, and inelastically

to that of Si 2s is used for curve fitting. The principal difference scattered background signal. Accounting for these three sources of
between Si 2p and Si 2s is that Si 2p involves doublet peaks with the signal is fundamental to accurate quantification by XPS.
significantly less Lorentzian character. Nevertheless, both peak
models in Figs. 11 and 12 provide excellent data reproduction, and F. Asymmetry parameters for metals and aromatic
the use of these lineshapes is supported by observing the consis- structures
tency achieved for chemical state component areas calculated from
Asymmetry is observed in photoemission data for a number
these peak models (inset table in Fig. 12). The asymmetric
of reasons. The origin of this asymmetry is multifaceted, including
Lorentzian (LA) lineshape used in this example is described in
instrumental influences, sample/measurement artifacts, the band
detail in recent reports.54,55
structure of the sample, and other physical reasons associated with
photoemission itself. Modeling asymmetric components is arguably
E. Including shake-up one of the more difficult problems related to peak fitting.54,57,58
For unsaturated carbon, which is often in aromatic rings, a Historically, asymmetry has been included in lineshapes via a
shake-up feature due to π–π* (HOMO–LUMO) transitions coming so-called exponential tail. The necessary form for including an
from the ring excited by the exiting photoelectrons must be considered. exponential tail is produced by blending the influence of an expo-
A peak model for PEEK (Fig. 13) includes features assigned as nential function with a lineshape with characteristics of a
shake-up signals typical of ring polymer spectra. The use of Lorentzian and/or a Gaussian resulting in a well-defined compo-
shake-up components in a peak model for PEEK is particularly nent area. Figure 14 illustrates one possible form for exponential
important for modeling the O 1s signal since a shake-up feature is tail modification to a Lorentzian lineshape, which was extensively
potentially beneath signal attributed to O—C O 1s. PEEK spectra are used when fitting polymer spectra within the Beamson and Briggs
The case of aluminum oxide on aluminum metal (Fig. 17) is

offered as an example of where relating metal and oxide intensities
measured by fitting components to data is the basis for estimating a
thickness for an oxide film on a metal substrate. In this example, a
lineshape is modified to simulate geometric aberration induced
asymmetry within measured photoemission lines. Figure 17 dem-
onstrates the use of a subtle but important asymmetry within
narrow metallic components. The peak model also includes a back-
ground generated by these metallic components, which is modeled
with the Shirley algorithm applied to the metallic components
only. The oxide background is modeled as linear. The model in
Fig. 17 represents a systematic tool for comparing intensity from
aluminum oxide and aluminum metal, from which film thickness
can be estimated using the Hill Equation.60
The mathematics of optimization suggests that making use of
lineshapes that best approximate photoemission shapes within a
peak model is important to chemical state determination. Using
lineshapes closest to observed peak shapes reduces the need to
enforce parameter constraints during optimization, bearing in
mind that the application of parameter constraints represents an
input of user bias to a peak model. A number of components and
FIG. 12. Si 2p data measured consecutively with the Si 2s data in Fig. 11 lineshapes are essential inputs to peak models, while parameter
modeled using lineshapes shown in the inset table that differ significantly from constraints should be considered nonessential inputs but required
those used for Si 2s. The background is approximated using a flat pedestal to compensate for imperfections in lineshapes, backgrounds, and
background upon which a component formed by computing a Shirley back- issues with signal-to-noise. There is, therefore, just cause to investi-
ground making use of elemental silicon components to compute the shape for gate asymmetric lineshapes other than the traditional forms, partic-
the Shirley response. The definition of lineshapes is described in Casa Software
manual (Ref. 56). Quantification is performed with Scofield cross sections. The ularly for situations where narrow components are involved, and
Effective Attenuation Length (EAL) Universal formula and the transmission func- instrumental artifacts have increased influence over observed peak
tion are defined by PHI. shapes.
G. Uniqueness plot
33
XPS of Polymers Database. Figure 15 is an example of a peak In this section, the impact of FWHM on a peak model is con-
model consisting of a single component making use of an exponen- sidered. The data analysis in Fig. 18, performed using a so-called
tial tail lineshape to fit an O 1s peak measured from Nylon 6 pre- uniqueness plot,61 shows that a range of plausible figure-of-merit
pared by cleaning with an argon cluster source ion gun. values is obtained through optimization involving specific FWHM
There are two aspects to fitting data using asymmetric line- values for the Ga 3s component. The uniqueness plot demonstrates
shapes, namely, data reproduction and quantification via a compar- how one can select an informed, fixed FWHM parameter for Ga 3s
ison of component area. The example shown in Fig. 16 illustrates for use in fitting curves to an individual spectrum as the only
one of these aspects. means of establishing a physically meaningful peak model.
The problematic lineshape used in Fig. 16 is a Doniach–Sunjic Each peak model includes parameters for peak position,
profile convoluted with a Gaussian, which certainly allows good data FWHM, and area. FWHM differs from position and area in the
reproduction, but fails to permit accurate quantification as a conse- sense that FWHM depends upon instrumental energy resolution,
quence of an extended asymmetric tail. Care should be taken when data acquisition conditions, as well as on the chemical state of the
using the Doniach–Sunjic lineshape, as component area changes as a sample. Ideally, the BE and relative area for the component peaks
function of the asymmetry parameter, and contributions from will be independent of the instrumental energy resolution.
higher BE components may overlap with an extended tail. Furthermore, there is correlated information between the lineshape
An example of where both data reproduction and quantifica- and FWHM in the sense that lineshape parameters chosen also
tion are important is measuring intensities for an oxide film over alter FWHW for the curve being fitted using the FWHM fitting
an elemental substrate, such as aluminum oxide on aluminum or parameter. By making a uniqueness plot, one can assess how a par-
silicon oxide on silicon. Separation of oxide signal from an elemen- ticular fitting parameter changes the outcome of curve fitting. This
tal signal is best performed using lineshapes for which adjustments technique is applied to the FWHM for the data and curves shown
to component parameters do not have significant consequences for in Fig. 18.
the component area, which is not the case for Doniach–Sunjic Optimization of the peak model shown in Fig. 18 was per-
profiles. For this reason, asymmetry in photoemission peaks is formed using optimization parameters that were free to adjust
typically modeled using lineshapes other than the Doniach–Sunjic within physically meaningful intervals. The standard constraint
profile.59 (discussed in Fig. 8) on the component areas of the S 2p doublet
FIG. 13. High-resolution C 1s and O 1s spectra of PEEK. The colors of the peaks correspond to the colors of the carbon and oxygen atom types in the repeating PEEK
polymer unit above. A background modeled the same was as in Figs. 11 and 12.
components was utilized in the original optimization model. One

means of testing the influence of FWHM on a peak model is to
specify a fixed FWHM value close to the value for the FWHM
resulting from the original optimization, then refitting the new
model to the same data. If repeated for a range of fixed FWHM
values, a set of solutions with a new figure-of-merit result. The plot
in Fig. 19 is that of a figure-of-merit plotted as a function of fixed
FWHM values for the Ga 3s component in Fig. 18. The curve in
Fig. 19 clearly shows a minimum in the figure-of-merit and signifi-
cant deviation away from the minimum. The flatter this curve, the
smaller the effect of the parameter on the fit. A flat curve in the
uniqueness plot can often indicate that the peak that it belongs too
is not appropriate for use in the peak model.
H. Curve-fitting data obtained with achromatic x rays

Lineshapes used in peak models are not necessarily transfer-
able between data collected from different instruments. The most
apparent differences occur for data collected using achromatic
x-ray sources compared to monochromatic x-ray sources. XPS
spectra collected with achromatic x rays are more complicated to fit
FIG. 14. Exponential tail lineshapes constructed using a Lorentzian profile mod-
due to the presence of an x-ray satellite structure. While many ified by an exponential form as described in Beamson and Briggs (Ref. 36).
modern XPS instruments use monochromatic x rays, there are still
FIG. 16. Multiwalled carbon nanotube C 1s data fitted making use of a

Doniach–Sunjic lineshape (Ref. 28). The definitions of potential lineshapes are
described in the Casa Software manual (Ref. 56). The peak model includes an
FIG. 15. O 1s signal from Nylon 6 modeled using an exponential tail modifica-
example of an active approach to modeling the background signal. These data
tion to a Gaussian/Lorentzian SGL (70) symmetric lineshape (CASAXPS equiv-
were acquired as a set of images using the imaging mode of an XPS instrument
alent of GLS M = 0.7 lineshape as discussed above). The definitions of potential
from which spectral data are processed. The residual standard deviation reflects
lineshapes are described in the Casa Software manual (Ref. 56). Following the
adjustments to the raw pulse counted signal performed on images within the
formation of the exponential tail lineshape, the resulting asymmetric profile is
original data set. These data represent an example of data for which the target
further convoluted with a Gaussian. The assumption in using an asymmetric tail
residual standard deviation is different from unity.
to model the O 1s measured from Nylon 6 is that the peak shape is a conse-
quence of measurement conditions rather than additional chemistry due to con-
tamination. The linear background was used.
I. Using complementary information from the valence

band region to assist the interpretation of the core
many instruments using achromatic x-ray sources. The energies of region
the x-ray satellites are well known, and to be effective, the curve fits The valence band region provides complementary information
need to include additional peaks for photoelectrons excited by to the core region since the appearance of the spectrum in this
these typically higher energy x rays. region is determined by the effect of chemical bonding and, in the
In most cases, up to seven peaks can be included for each of case of many materials, especially metals, the extensive dispersion
the principal XPS peaks, these peaks corresponding to photoelec- of the electron energy levels. This leads the valence band region to
trons ejected by Kα1,2, Kα0 , Kα3, Kα4, Kα5, Kα6, Kβ x rays. Since have a complex spectral shape where curve fitting is not as simply
curve fitting is generally conducted over a narrow energy range performed for the analysis of valence band as it is in core-level
(e.g., 10–25 eV), only the Kα0 , Kα3, Kα4 x-ray satellites typically XPS. Overlays of the ground state density of states calculated using
need to be included. Peaks excited by Kα0 , Kα3, Kα4 x rays have first-principles band structure theory,64 or in suitable cases by
intensities representing about 1%, 8%, and 6%, respectively, of the cluster calculations, can be quite useful in interpreting valence
intensity of the main peak and are at 4.6, 8.4, and 10.2 eV lower BE band spectra. A study of the often complex shape of the valence
than the principal peak. The other higher energy x-ray satellites band region can assist identification since it is the pattern that is
need to be included when a wider energy range is fitted, for characteristic of the material so that errors in calibration and thus
example, for a 50 eV range to cover the two spin–orbit split Ag 3d BEs are less of an impediment to the correct interpretation of the
peaks.62 Information for x-ray satellite energies and relative data than they are in the core region. In other words, the valence
intensities can be obtained from x-ray emission spectra29,63 or from band region can be a useful “fingerprint” for identifying materi-
XPS studies.62 als.65 Listed below are some examples where the valence band
FIG. 17. Al 2p spectrum measured by John Walton (University of Manchester) FIG. 18. A material including sulfur and gallium results in spectra with overlap-
from an aluminum foil. An asymmetric lineshape is applied to the narrow alumi- ping component peaks for S 2p and Ga 3s. These component peaks are exam-
num metal 2p doublet components while the oxide components are generalized ples of photoemission with significantly different lineshapes and significantly
Voigt functions. (Ref. 54) The definition of lineshapes is described in Casa different FWHM fitting parameter values. The definition of lineshapes is
Software manual (Ref. 56). A Shirley background is computed using the metal described in the Casa Software manual (Ref. 56). Four-parameter universal
components, which only allows a flat background beneath the aluminum oxide cross section Tougaard background is used.
components. Note how both the aluminum oxide and aluminum metal signals
interact with each other via Lorentzianlike tails to these lineshapes.
o Carbonates and bicarbonates can be distinguished.69
o Different types of phosphates show no difference in the P 2p
region can be especially effective in the identification of different core region, but substantial differences in the valence band
chemical species, where this is particularly true when monochro- region (Fig. 20).70,71
matic X-radiation is used: • Polymers typically give a valence band that is rich in features.
Thus, organic polymers with little or no difference in the C 1s
region often show a valence band with very characteristic
• Metals often have very distinct features in the valence band
features.36
region, for example:
o Molybdenum metal has a distinct four feature pattern at BEs
below 5 eV, which can be explained by the calculated
spectrum.21,66
• Silver metal has a distinct four feature pattern at BEs below 8 eV, J. Reporting of fitting process and parameters
which can be explained by the calculated spectrum.21 To enable others to understand and assess the results obtained
• Oxides often have distinct valence band features, including a from fitting of spectra, it is necessary that both the results and
multiple peak pattern in cases where the core region exhibits one information about the fitting approach, constraints, and assump-
peak with little or no BE shift between different oxidation states, tions and final fitting parameters be included in journal articles or
for example: reports. ISO Standard 19830 describes the minimum reporting
o Molybdenum oxides have distinctly different valence band requirements for peak fitting in XPS.72 Important parameters
spectra.21,67 include spectrometer and x-ray characteristics, the use of charge
o Aluminum oxides and oxyhydroxides cannot reliably be distin- compensation and charge correction, the type of spectral
guished in the Al 2p core region but show substantial differ- pre-preprocessing such as satellite subtraction, smoothing, and
ences in the valence band region.64,68 deconvolution, the type of background used, fitting parameters
• Molecular ions such as sulfates, carbonates, and phosphates have such as lineshapes, FWHM, and χ2, as well as the software used for
distinguishable valence band features, for example: curve fitting.
For the full list of minimum reporting parameters, please refer

to ISO,72 while here we include some of the recommended parame-
ters. On the experimental side, the photon energy and the type of
source (monochromatic or achromatic) should be listed. The type
of analyzer and the geometry of the measurement should be
described, including the expected resolution of the measurement.
Finally, the form of the sample (solid, thin-film, powder) should be
given. On the fitting side, the fitting parameters should be given in
detail, including a description of the backgrounds used in the fit.
Lineshapes and linewidths should be documented. If linewidths
used vary significantly across a spectral fit, an explanation of why
this is physically reasonable should be included. The software used
in the analysis should be listed. Spectra should have a complete
core level spectral range to include background and spin–orbit
components. Tables of parameters, including error bars, will make
the fitting information more accessible to the reader.
VII. SUMMARY AND CONCLUSIONS

As the use of XPS data in many areas of science and technol-
ogy has become increasingly important, and the complexity of
advanced materials has increased, the extraction of important phys-
icochemical information increasingly requires the fitting of XPS
FIG. 19. Uniqueness plot based on scanning the Ga 3s FWHM for a range of data. Unfortunately, the processes used and the information
fixed values in an interval of 1.3–3.0 eV. The FWHM achieved by optimization for obtained are often incorrect or incomplete,3 and information asso-
the model in Fig. 18 is 2.0 eV. Note the figure-of-merit is within the range for all ciated with fitting processes and results is often not adequately
FWHM that would be acceptable as an indication of good data reproduction by a reported. The good practices and information presented in this
peak model, but the best value is clearly observable in the uniqueness plot.
guide are provided as a guide to improving the quality of the XPS
curve fitting reported in the literature.
One of the main objectives of the curve fitting of XPS data is
to extract chemical information about the sample being examined.
Consequently, curve fitting needs to be done in a manner that is
consistent with the physics and chemistry of both the XPS process
and the specimen being examined. It is also important to remem-
ber that the quality of chemical information extracted depends on
the quality of data acquisition and data processing.
Many errors related to fitting and peak identification in the lit-
erature arise from authors not recognizing the impacts of not only
intrinsic but also extrinsic phenomena, such as spin–orbit splitting
or the effects of plasmons, multiplet splitting, or shake-up pro-
cesses. The XPS peak positions and lineshapes are significantly
affected by these processes. Such effects highlight the importance
of relevant reference spectra in the understanding and fitting of
peak structures.
In the application of curve fitting to XPS spectra, reference
materials, consistency of approach to both reference and target
materials, paying attention to the physics and chemistry of the pho-
toelectron peaks, and appropriate reporting of the approach, soft-
ware used, and fitting parameters are all critical. This guide has
provided a summary of important issues and described tools and
strategies that represent good practices important to useful, infor-
mative, and reproducible peak fitting of core-level XPS spectra.
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Practical Guide For Curve Fitting in XPS

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Practical guide for curve fitting in x-ray

George H. Major, Neal Fairley, Peter M. A. Sherwood, et al.

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TABLE I. Table of commonly observed errors in XPS peak fitting.

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Error Details How to avoid Reference

Error Details How to avoid Reference

2. Linewidth of the x rays used to eject the

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FIG. 11. Si 2s measured using a PHI Quantum 2000 monochromatic Al x-ray

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