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Applied Surface Science 326 (2015) 151161

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Applied Surface Science


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

Generalized molybdenum oxide surface chemical state XPS


determination via informed amorphous sample model
Jonas Baltrusaitis a,b, , Beatriz Mendoza-Sanchez c , Vincent Fernandez d , Rick Veenstra b ,
Nijole Dukstiene e , Adam Roberts f , Neal Fairley g
a
Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015, USA
b
PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217,
7500 AE Enschede, The Netherlands
c
CRANN, Chemistry School, Trinity College Dublin, Dublin, Ireland
d
Institut des Matriaux Jean Rouxel, 2 rue de la Houssinire, BP 32229, F-44322 Nantes Cedex 3, France
e
Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas, Lithuania
f
Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP, UK
g
Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE, UK

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

Article history: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial
Received 4 July 2014 importance in many science and engineering disciplines, including chemistry, fundamental and applied
Received in revised form surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is
14 November 2014
the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can
Accepted 16 November 2014
be subject to incorrect interpretation. Unlike traditional XPS spectra tting procedures using purely syn-
Available online 22 November 2014
thetic spectral components, here we develop and present an XPS data processing method based on vector
analysis that allows creating XPS spectral components by incorporating key information, obtained exper-
Keywords:
X-ray photoelectron spectrometry
imentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation
Spectra envelope states and degree of crystallinity, were processed using this method and the corresponding oxidation
Molybdenum oxide states present, as well as their relative distribution was elucidated. It was shown that monitoring the
Informed amorphous sample model evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray
probe could be used to infer solutions to complex spectral envelopes.
2014 Elsevier B.V. All rights reserved.

1. Introduction The most important and commonly found are molybdenum tri-
oxides and molybdenum dioxides. The former includes the layered
Molybdenum oxides are important materials exhibiting wide orthorhombic -MoO3 and the monoclinic -MoO3 , the latter is
range of chemical and physical properties suitable for many labora- a monoclinic rutile type structure, made of edge sharing MoO6
tory and industrial applications. Due to the presence of delocalized octahedra [19,20]. The oxygen decient perovskite structure of
4d electrons, molybdenum oxides exhibit electrochemical, pho- MoO3 allows for an efcient intercalation of ions altering its optical
tochemical and catalytic properties that are of high interest for and charge storage properties [9]. MoO3 is stable and relatively easy
broad range of applications, including heterogeneous chemistry to prepare whereas preparing stable and stoichiometric MoO2 is
and catalysis [13], photo- and electrocatalysis [46], batteries more difcult due to the need to maintain a highly-controlled oxy-
[7,8], supercapacitors [912], sensors [13,14], as well as photo- gen partial pressure during Mo-metal oxidation [20]. The Mo (V)
voltaic [15,16] and electro- and photochromic applications [17,18]. oxide, Mo2 O5 , also possesses interesting electrochromic proper-
Since molybdenum can have a wide range of oxidation states ties but is typically unstable in its pristine form [21]. Incorporation
ranging from +2 to +6, a variety of its oxide compounds exist. of small atoms, such as hydrogen, alkali metals or water between
the MoO3 layers allows for stabilization of the Mo (V) state via
coordination of the guest atom to the metal center [21].
The chemical and electronic properties of molybdenum oxides
Corresponding author at: Department of Chemical Engineering, Lehigh Univer-
are determined by the oxidation state of the molybdenum atom
sity, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015, USA.
Tel.: +1 610 7586836. and thus its precise determination and control is of crucial impor-
E-mail address: job314@lehigh.edu (J. Baltrusaitis). tance for many applications. Molybdenum oxides are pervasive

http://dx.doi.org/10.1016/j.apsusc.2014.11.077
0169-4332/ 2014 Elsevier B.V. All rights reserved.
152 J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161

materials in catalysis, e.g. MoO2 catalyzes hydrocarbon reforming 2. Experimental and data analysis
due to its metallic conductivity [2,22]. MoO2 based catalysts for
hydrocarbon oxidation are typically prepared via in situ reduction 2.1. Materials
of MoO3 and the degree of Mo (VI) to Mo (IV) conversion deter-
mines the resulting catalytic properties. Guilln-Villafuerte et al. Molybdenum dioxide (MoO2 , 99% purity) was purchased from
[23] showed large differences in electrochemical direct methanol Alfa Aesar; ammonium molybdate tetrahydrate ((NH4 )6 Mo7 O24
fuel cell performance of a coreshell molybdenum oxide particle 4H2 O, 99% purity), sodium molybdate dihidrate (Na2 MoO4 2H2 O,
catalyst where the core was Mo or MoO2 and the shell was MoO3 . 99% purity), sodium hydroxide (NaOH, 99% purity) and sulfuric
The reduced Mo phase in the core produced electronic effects which acid (H2 SO4 , >98% purity) from Sigma; ammonium sulphamate
determined the catalytic activity and stability during the electro- (NH4 SO3 NH2 > 98% purity) from Lachema, Czech Republic. Double
oxidation processes [23]. Furthermore, amorphous molybdenum distilled water (DI-water) was used for all the synthesis protocols.
oxide lms exhibit better photochromic properties than crystalline
ones, thus being more suitable for memory devices [24,25]. This 2.2. Molybdenum oxide samples
phenomenon led to an almost empirical formulation of the manu-
facturing strategies to synthesize molybdenum oxide lms with the Three samples were used in this work: (1) as-purchased MoO2
best electro- and photochromic performance. Notably, substoichio- powder, (2) crystalline MoO3 thin lms prepared by spray pyrolysis
metric amorphous lms yielded blue color associated with oxygen deposition (Section 2.2.1), and (3) amorphous molybdenum oxide
vacancies in MoO3 lm [24]. This color has also been associated lms prepared by electrodeposition (Section 2.2.2).
with Mo (V) oxide, Mo2 O5 , as oxygen vacancies usually result in
the two unpaired electrons that have been known to yield reduced 2.2.1. Spray pyrolysis deposition of crystalline MoO3 thin lms
Ti(III) species in TiO2 [26]. These observations show that for any MoO3 thin lms were prepared by spray pyrolysis deposition
possible molybdenum oxide application, obtaining, correctly inter- following established procedures [36,37]. Ammonium molybdate
preting and understanding the molybdenum atom oxidation state tetrahydrate ((NH4 )6 Mo7 O24 4H2 O, 0.15 g/ml wt/wt) was used as a
is of utmost importance. precursor. The deposition was done onto ITO substrates maintained
The oxidation state of a certain metal in any material surface can at 350 C. Post-deposition annealing was done at 500 C.
be determined using X-ray photoelectron spectroscopy (XPS). Here,
the probing depth is determined by the inelastic mean free path of 2.2.2. Electrodeposition of the amorphous molybdenum oxide
the electron and typically is a few nanometers [27,28]. Molybde- lms
num oxide surfaces of varying chemical composition, complexity, Electrodeposition was carried out at room temperature
crystallinity and intercalation have been extensively analyzed via (22 2 C) in a conventional three-electrode JCE-2 cell using a stain-
XPS [4,6,11,21,22,2934]. The exact and accurate interpretation of less steel plate (1 cm 2 cm) as working electrode, a platinum spiral
the results obtained, however, has been poorly addressed in the wire as counter electrode (12.5 cm2 active area), and an Ag|AgCl
literature due to the complexity of the XPS spectra, particularly |KCl(sat) as reference electrode. A computer-controlled Autolab
when samples include different oxidation states. In this case, each PGSTAT12 (Ecochem, the Netherlands) potentiostat/galvanostat
oxidation state gives origin to a different Mo 3d spectral compo- was used. Prior to electrodeposition, the surface of the stainless
nent [11]. Additional components contributing to the XPS signal steel plate was mirror-polished with Emery paper and cleaned
may arise due to exposure of samples to the atmosphere. with detergent, DI-water, and by dipping in HCl (50% in water,
Scanlon et al. [29] did a thorough XPS analysis of MoO3 and for 5 min at 65 C). The stainless steel plate was then rinsed
MoO2 samples with well-dened crystal structure and nearly per- with DI-water and immediately transferred to the electrochemi-
fect stoichiometry. Although this study constitutes a good starting cal cell. The electrolyte used for deposition was sodium molybdate
point in the understanding of XPS spectra of molybdenum oxides, dihydrate (Na2 MoO4 2H2 O, 0.2 M) using ammonium sulphamate
the general problem is far more complex when samples subject to (NH4 SO3 NH2 , 0.22 M) as supporting electrolyte. The pH of the elec-
different modications altering their chemical composition and/or trolyte was adjusted to 6.5 (adding either 1 M H2 SO4 or 6 M NaOH
crystal structure are involved. The problem involved in the correct solutions). A fresh plating bath was prepared for each electrode-
interpretation of XPS spectra of molybdenum oxides is illustrated position experiment. Immediately after the electrodeposition, the
by the case of MoO2 . Currently, there is no consensus about the electrodeposited lms were thoroughly rinsed twice with DI water,
spectral components of the XPS spectrum of MoO2 . In most reports followed by dipping in ethanol and then held in a desiccator over
to date, Mo (IV) in MoO2 spectrum is modeled using a single pair the silica gel for at least 2 h. Sample thickness was measured using
of doublet peaks [22,35]. However, Scanlon et al. has shown that optical microscopy and determined to be 800 nm. Samples were
the spectral component corresponding to a Mo (IV) oxide is not a labeled P3-1, P3-2 and P3-3 corresponding to deposition potentials
simple doublet pair, but consists of two doublets corresponding to of 0.7, 0.9 and 1.1 V, respectively.
screened and unscreened environments for the Mo (IV) electronic
state [29]. A degree of complexity is added if other oxidation states 2.3. XPS analysis and data processing
are involved, such as the presence of Mo (VI) oxide, proved to be
rather common [29]. 2.3.1. XPS sample measurements
In this work, we use a divide-and-conquer strategy to address the X-ray photoelectron spectroscopy (XPS) analysis was performed
interpretation of complex XPS spectra of molybdenum oxides. We using either a Kratos Axis Nova (University of Nantes, Nantes,
synthesized and analyzed a range of molybdenum oxide materials France) instrument or a Kratos Axis Ultra (Kratos Analytical Limited,
of varying oxidation states and crystallinities. A series of periodic Manchester, UK).
XPS measurements of a crystalline -MoO3 were used to provide a
range of spectra for which complex data envelopes can be examined 2.3.1.1. Settings for measurements using the Kratos Axis Nova
using mathematical modeling techniques allowing to identify the (University of Nantes, Nantes, France). The instrument used a
building blocks (vectors) required to t XPS spectra. Those build- monochromated Al K source 1486.6 eV. The instrument base
ing blocks were then utilized in the elucidation of oxidation states pressure was 5 1010 Torr. The instrument calibration was done
of a MoO2 sample and a series of amorphous molybdenum oxide following the procedure by Seah et al. [38]. The sample area ana-
samples. lyzed was about 700 m 300 m. A pass energy (PE) of 80 eV,
J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161 153

Fig. 1. XRD patterns of (a) electrodeposited amorphous molybdenum oxide, (b) spray pyrolysis-deposited MoO3 and (c) as-purchased MoO2 samples.

corresponding to an all over Fermi edge resolution of 0.89 0.02 eV source. Operating pressure of the spectrometer during data acqui-
with a 0.5 eV step, was used to acquire wide range survey spectra. sition was 5 109 Torr.
A PE of 20 eV, corresponding to an all over Fermi edge resolution of
0.39 0.02 eV with a 0.1 eV step, was used to acquire narrow spec-
2.3.1.3. Periodic measurements of the MoO3 , MoO2 and amorphous
tra of the Mo 3d, C 1s, O 1s, Mo 4p, and Mo 4d orbitals. A PE of 40 eV,
molybdenum oxide samples. The MoO3 , MoO2 and amorphous sam-
corresponding to an all over Fermi Edge resolution of 0.56 0.02 eV
ples were continuously exposed to X-rays while continuously using
with a 0.15 eV step, was used to acquire spectra at the valence band
a charge neutralizer. The MoO3 sample was measured using a Kratos
energy region. All data were acquired using charge compensation
Axis Nova (University of Nantes, Nantes, France) and was exposed for
to establish a steady state surface potential.
a total time of 577 min with spectra acquisition every 15 min (a total
of 39 measurements). The spectra acquisition of the Mo 3d, C 1s, O
2.3.1.2. Settings for measurements using the Kratos Axis Ultra 1s, Mo 4p, and Mo 4d regions consisted of three scans with a dwell
(Kratos Analytical Limited, Manchester, UK). Monochromated Al time per energy channel and per scan of 0.15 s. The spectra acqui-
K excited X-ray photoelectron spectra were acquired from a sition of the valence band energy region consisted of one scan with
700 m 300 m analysis area with X-ray power of 450 W (30 mA, a dwell time per energy channel and per scan of 0.15 s. The amor-
15 kV). Survey spectra were acquired at 160 eV pass energy and phous molybdenum oxide sample P3-2 was measured using the
narrow region spectra acquired at 20 eV pass energy, with typical same instrument and the same acquisition parameters used for the
acquisition times of 120 s and 180 s respectively. Where required, MoO3 sample. The MoO2 sample was measured using a Kratos Axis
charge compensation was achieved using a low energy electron Ultra (Kratos Analytical Limited, Manchester, UK) and was exposed
154 J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161

to X-rays for a total time of 170 min with spectra acquisition every
13 min (a total of 12 measurements). The spectra acquisition of the
Mo 3d, C 1s, O 1s, Mo 4p, and Mo 4d regions, as well as the valence
band binding energy region, consisted of one scan with a dwell time
per energy channel and per scan of 0.2 s.
The amorphous molybdenum oxide samples P3-1, P3-2 and
P3-3 were measured using a total acquisition time of 7 min. No
charge neutralization was performed for these samples as none was
required to maintain peak resolution and shape.

2.3.2. Data processing


XPS data including peak tting, line shape synthesis, enve-
lope background modeling and subtraction, Monte Carlo analysis,
quantication of components and plotting, was processed using
a CasaXPS program (suite version 2.3.17). The acquired spectra
required a binding energy calibration based on identifying a com-
ponent peak within a data envelope. The procedure adopted was
based on aligning a component peak within the O 1s spectrum
rather than the more usual alignment based on a component within
the C 1s spectrum. Charge referencing was achieved by locating
the peak maximum for a component line shape derived from the
MoO3 crystalline sample for the O 1s peak to a binding energy of
530.45 eV. The principal data treatment steps are described in the
context of the experiment in Section 3.2.

3. Results and discussion


Fig. 2. Mo 3d and valence band spectra (insets) acquired at various times (minutes),
3.1. XRD analysis of molybdenum oxide samples indicated in brackets, of X-ray exposure of (A) MoO2 and (B) MoO3 .

XRD patterns of electrochemically synthesized (amorphous), as


invasive X-ray probe. These changes were signicantly less dras-
well as crystalline MoO3 and MoO2 samples used in this work are
tic for the MoO2 sample. No signicant changes were observed in
shown in Fig. 1ac, respectively. The electrochemically deposited
the C 1s and O 1s spectra. Consistent with our studies, Scanlon
molybdenum oxide showed peaks only due to the stainless steel
et al. [29] reported that the binding energies for the O 1s peaks
substrate and did not possess any distinct crystalline habit. The
of MoO2 and -MoO3 differed by 0.2 eV and had almost identical
spray pyrolysis-deposited molybdenum oxide sample showed
Full-Width-Half-Maximum (FWHM), while the corresponding Mo
prominent reections from the (0 2 0), (1 1 0), and (0 4 0) and (0 2 1)
3d spectra had signicant binding energy shifts and different peak
planes assigned to orthorhombic -MoO3 (JCPDF card 75-912).
structure. It is worth to notice that the acquisition of XPS spectra
It has been previously shown that annealing at low tempera-
shown in Fig. 2 was done with samples previously exposed to the
tures (200300 C) results in formation of metastable monoclinic
atmosphere (ex-situ conditions) and thus the data envelopes are
-MoO3 phase, whereas higher temperatures (>400 C) yield crys-
likely to include components associated with changes in the sam-
talline orthorhombic -MoO3 phase [39]. Finally, the as-purchased
ple induced by exposure to oxygen. As described later, according to
MoO2 was found to possess a monoclinic crystalline phase with
the XPS tting models here proposed, the MoO2 sample seemed to
(1 1 1), (2 0 0) and (0 0 2) being the most prominent reections
have a MoO3 surface layer. Supporting this nding, it has been pre-
(JCPDS card 33-0929).
viously reported that the Mo 3d spectrum of a MoO2 sample may
include components corresponding to MoO3 [29].
3.2. XPS degradation studies of MoO2 and -MoO3 samples As shown in Fig. 2A, the exposure to X-rays of the MoO2 sample
did not originate any new components. In the case of the -MoO3
Samples of MoO2 and -MoO3 (prepared by spray pyrolysis- sample, before a signicant X-ray exposure (0 min exposure time),
deposition) were continuously exposed to X-rays while acquisition the Mo 3d5/2 peak was at 232.5 eV (Fig. 2B) and was assigned to
was performed periodically. The MoO2 sample was measured for a Mo (VI). This is consistent with the literature reporting a bind-
total time of 170 min with spectra acquisition every 13 min (a total ing energy of 232.38 eV for the Mo 3d5/2 peak of -MoO3 [29,32].
of 12 measurements). The -MoO3 sample was measured for a total As shown in Fig. 2B, as X-ray exposure progressed, the new Mo
time of 577 min with spectra acquisition every 15 min (a total of 39 3d spectra appeared to incorporate a new spectral component at
measurements). Narrow scans at binding energy intervals associ- low binding energy. The Mo 3d spectrum measured at an exposure
ated with the Mo 3d, C 1s, O 1s, Mo 4p, and Mo 4d orbitals, as well time of 566 min (black spectrum in Fig. 2B) had a Mo 3d5/2 peak at
as the valence band spectra were acquired. 231.8 eV and could be due to Mo (VI) reduction into a lower oxida-
tion state component. As discussed earlier, the peak at 231.8 eV has
3.2.1. XPS spectra of MoO2 and -MoO3 been assigned to Mo (V) [32], but the true origin for the doublet is
Fig. 2 shows the XPS spectra in the Mo 3d and valence band not certain.
energy regions of MoO2 (at 27 min and 160 min acquisition time) As shown in Fig. 2B, the Mo 3d doublet of the just measured
and -MoO3 (at 0 min, 89 min and 566 min acquisition time). The -MoO3 sample (0 min) showed a degree of asymmetry at approx-
spectra of MoO2 and -MoO3 were clearly distinctive. Most impor- imately 237.5238.0 eV. This asymmetry diminished with each
tantly, the Mo 3d and the valence band spectra of both samples acquisition cycle while the new spectral component at low bind-
showed an evolution of shape over acquisition time suggesting ing energies described above became apparent. At 89 min of X-ray
structural and chemical alterations of the samples caused by the exposure, the Mo 3d spectrum stabilized in terms of asymmetry to
J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161 155

high binding energy while retaining the new spectral component exposure within the data set acquired over 39 measurement cycles
appearing at lower binding energy. The origin of the asymmetry recorded using 577 min of acquisition time. The data processing
at high binding energies is unknown. We speculate that it could here followed involves the following steps: (1) identication of
be sample surface contamination that gets degraded over X-ray a subset of spectra that can be mathematically described using
exposure. only two principal components or spectral forms and (2) repro-
The valence band XPS spectra of MoO2 and MoO3 exhibited duction of the entire data subset by using linear combinations
the shape characteristic of the metallic behavior of MoO2 (inset of of these two spectral forms only. The rst step uses a standard
Fig. 2A) and the wide bandgap semiconducting behavior of -MoO3 linear Principal Component Analysis (PCA) procedure while the
(inset of Fig. 2B). The peak at 12 eV in the valence band spectra of second step uses a standard non-linear optimization procedure
-MoO3 could be due to oxygen vacancies increasing with X-ray (Marquardt [44] or Simplex algorithms [45]) to nd the appro-
exposure [40]. priate spectral forms that can be used as components in a peak
model. Other than demonstrating the selected set of spectra belong
3.2.2. Challenges faced during XPS analysis of molybdenum oxide to the same 2D subspace, PCA is not important to the data treat-
samples ment.
A Mo 3d doublet, having spinorbit components Mo 3d5/2 and
Mo 3d3/2 , is frequently associated with a single oxidation state 3.2.3.1. Selection of a subset of spectra. First, by applying a PCA
in molybdenum oxides. The available literature suggests that the (described in the Supplemental Information Section S2) to the
Mo 3d5/2 peak binding energies corresponding to the oxidation -MoO3 data set, a MoO3 subset of spectra (MO3SS), that can be
states Mo (VI), Mo (V) and Mo (IV) and Mo are at 232.5232.6 mathematically described using only two principal components u1 ,
[29,32], 231.6 [32], 229.1229.3 [29,32] and 228.3 [29] eV, respec- and u2 , was identied. From within the identied MO3SS two spec-
tively. Table 1 summarizes values reported in the literature. These tral forms v1 , and v2 were selected. The spectral forms v1 , and v2
very close binding energy assignments along with the correlated must exhibit contrast due to a physical or chemical process giving
nature of the Mo 3d doublets make the elucidation of the composi- origin to the variability of the MO3SS, in this case, the degradation
tion of samples, containing mixed oxidation states, a non-trivial processes due to the X-ray exposure. If v1 , and v2 are not suf-
procedure. This problem has been illustrated by the work of ciently different, the optimization procedure, described in the next
Mendoza-Snchez et al. [11], where XPS analysis of molybdenum paragraphs, will not return a well-dened solution. Examples of
oxide samples with mixed valence states showed complex XPS spectral forms sufciently different are those in Fig. 2B where the
envelopes. differences are due to the X-ray degradation process.
The key to develop a meaningful XPS model is the elucidation of
spectral components that are informative of the nature of the sam- 3.2.3.2. Optimization procedure for the construction of spectral com-
ple. Traditionally, synthetic components are created using imposed ponents. In order to aid the selection of appropriate spectral forms
constrains such as a specic binding energy, FWHM and relative v4 , as explained below, the spectral forms v1 , and v2 considered
peak intensity. These constrains are frequently a guess coming not only the Mo 3d binding energy regions but also the O 1s, C 1s,
from knowledge of the sample. Alternatively, some spectral com- Mo 4p and valence band binding energy regions, which for conve-
ponents can be built on the basis of known spectra of suitable nience were shifted to abscissa values close to the binding energy
standard samples. When little is known about the sample and no for the Mo 3d region.
standards exist, building a synthetic model becomes a challeng- The rst step was a background signal correction. A background
ing task. Considerable errors can be introduced during the tting signal for each spectrum v1 , and v2 was calculated and subtracted
process [41,42]. Moreover, quantitative sample analysis critically from the v1 , and v2 signal resulting in the spectral forms v1 , and
depend on constrains. For instance, as shown in the Supplemental v2 shown in Fig. 3B. Next, a numerical analysis procedure, illus-
Information Section S1, the proportion of given oxidation state in a trated in Fig. 3A, was followed. Given the vectors v1 and v2 , a vector
sample of mixed oxidation states, changes substantially when the v3 = v2 + v1 was calculated and utilized to assess the suitabil-
FWHM of a spectral component changes slightly from 1.0 to 1.08. ity of a vector v4 = v2 + v1 to t the spectra in the experimental
Therefore, synthetic models based on constrains, often assigned data subset MO3SS. Here and are constants calculated using a
with a high degree of uncertainty, may lead to misinterpretation non-linear procedure (Marquardt [44] or Simplex algorithms [45]).
of physical, structural and chemical phenomena occurring on the The spectral forms v4 are mathematically equivalent to the original
sample. spectra v1 and v2 and retain physically meaningful spectral struc-
In this work, we developed a methodology to extract tting ture of the MO3SS. This procedure was systematically repeated
spectral components from a set of experimental data. Importantly, generating a set of (,) values to compute v4 spectral forms and
these components are non-synthetic and not arbitrarily chosen, but compared against the experimental data until a satisfactory answer
because they are extracted from experimental data, they are infor- was found.
mative of physical processes occurring on the sample. It is known The criteria to select satisfactory spectral forms v4 were: (1) lin-
that X-ray exposure of metal oxides results in the generation of new ear combinations of spectral forms v4 should reproduce the entire
reduced metal oxides [43]. Here, we exposed a -MoO3 sample to initial data subset MO3SS and (2) the spectral forms v4 should
X-rays and measured a series of XPS spectra at periodic time inter- reveal information about the chemistry, for instance, oxidation
vals. The series of XPS spectra generated show variations uniquely states, not obvious in the initial data subset MO3SS. The selection of
due to physical, structural and chemical changes induced by the spectral forms v4 was a trial and error process of qualitative com-
invasive X-ray robe. As described in the next section, using this set parison of spectral forms v4 against experimental data. This was
of spectra we can extract meaningful spectral components informa- coupled to an element of judgment about the sample chemistry. It
tive of a specic change in the sample. Those spectral components should be noticed that many pairs of spectral forms v4 (I) and v4
can then be used to analyze other samples of similar or suspected (II) can be computed with the ability to reproduce a given spectrum
similar nature. in the MO3SS, however, not all of them offer physically meaning-
ful sample information. In order to aid the selection of appropriate
3.2.3. Derivation of spectral components of the -MoO3 data set vectors v4 , the spectral forms v1 and v2 considered not only the
We focus now on the analysis of the -MoO3 sample data Mo 3d binding energy regions but also the O 1s, C 1s, Mo 4p and
set. We considered the evolution in spectral shapes due to X-ray valence band binding energy regions. The spectral forms v4 then are
156 J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161

Table 1
XPS binding energy values for the Mo 3d spin orbital component of molybdenum oxides at various oxidation states.

Reference Sample Mo 3d 3/2 (eV) Mo 3d 5/2 (eV)

Mo (0) Mo (+4) Mo (+5) Mo (+6) Mo (0) Mo (+4) Mo (+5) Mo (+6)

[53] MoO3 235.6 232.5


MoO3 reduced 233 235.4 229.9 232.3
MoO2 233.1 235.4 230 232.3
MoO2 reduced 233.2 234.3 235.7 230.1 231.2 232.6
MoO2 reduced 233.1 234 235.6 230 230.9 232.5

[54] MoO3 235.44 232.32


[55] MoO3 /Mo mix 228.1 230.1 232.7
[56] MoO3 /Al2 O3 supported 235.5236 232.3232.8
[57] Mo/Au 231.5 228.3
Mo, MoO2 /Au 231.5 234.1 228.3 230.8
MoO3 /Au 235.8 232.7
MoO3 , Mo2 O5 /Au 234.6 235.8 231.5 232.7
MoO3 /Al2 O3 , TiO2 catalysts 232.1232.7

[58] 233235
[32] 234.8 231.6
[29] MoO3 235.63 232.48
MoO2 screened 232.47 229.27
MoO2 unscreened 234.21 231
Mo metal 231.49 228.29

[21] Mo2 O5. H2 O 234.9 231.5


[59] 233 235 236.1 229.9 231.9 233
[30] 234.92 236.29 231.78 233.15

suitable to reproduce all those spectral regions and not only the Mo only. In making this approximation it was assumed that the MoO3
3d spectral region. contamination of the crystalline MoO2 had degraded similarly to
Fig. 3B shows an illustration of the process of the computation the degradation process undergone by the -MoO3 sample. Then,
of spectral forms v3 and v4 from v1 and v2 . All the spectral forms additional synthetic Lorentzian-asymmetric (LF) [46] line shapes
included intensities from the Mo 3d, O 1s, C 1s, Mo 4p and valence were added, four to represent Mo 3d5/2 components and four to
band binding energy regions. The spectral forms v1 and v2 exhibited represent Mo 3d3/2 components. These synthetic components were
deformation due to the X-ray degradation deviating from the ideal introduced as a construction step rather than a physical model and
shape of the Mo 3d doublet of -MoO3 . Fig. 3B.4 and B.5 shows the were constrained only in terms of relative spinorbit splitting of the
construction of the spectral forms v3 (red area) and v4 (green line), Mo 3d doublet (ratio 3:2). The Mo 3d5/2 peaks (green lines labeled
from spectral components v2 (black line) and v1 (blue line), the as 1, 2, 3 and 4) and Mo 3d3/2 peaks (merged as a single green line)
latter shown as negative. The spectral forms v1 and v2 were are shown in Fig. 4A. The model was then tted and the resulting
selected due to apparent chemical signicance so that the spec- synthetic spectral line shape was compared against the various Mo
tral form v4 retained features open to physical interpretation. The 3d spectra from the MoO2 data set. This approach is only plausible
selected spectral form v4 was attributed to the XPS spectral compo- due to the availability of multiple spectra with evolving structure
nent of the Mo (VI) oxidation state, v4-Mo (VI). A similar procedure against which the generated models can be compared. Once a con-
was followed in order to select a second appropriate spectral form sistent model with the experimental data emerged, the Mo 3d5/2 LF
v4 to account for the spectral component resulting from the X- synthetic components were summed to form a single complex line
ray degradation and likely attributed to Mo (V), v4-Mo (V). Fig. 3C shape shown in Fig. 4B (green line). Scanlon et al. [29] proposed
shows a tting of a spectrum of the MO3SS with spectral forms the existence of satellite peaks for MoO2 . The model proposed in
v4-Mo (V) and v4-Mo (VI). Here the spectral forms v4-Mo (V) and Fig. 4B is consistent with this assumption but offers an alterna-
v4-Mo (VI) are meaningful components that exhibit degradation tive structure for the MoO2 peak model in terms of satellite peak
deformation due to the X-ray exposure and are able to t all the contributions.
spectra of the MO3SS.

3.2.4. Derivation of spectral components of the MoO2 data set 3.2.5. Summary and components quantication
Next, we analyzed the MoO2 data set. A rst step was the identi- In summary, the mathematical models here generated proposed
cation of binding energy regions possibly due to MoO3 which was components attributed to Mo (VI) and a component that could be
likely to occur due to exposure of the sample to the environment tentatively assigned to Mo (V) species in the -MoO3 sample. In
[29]. The MoO2 data set did not include sufcient spectra variation the case of the MoO2 sample, Mo (VI), tentatively Mo (V) and Mo
required for the procedure followed in the previous section for the (IV) species were identied. Next, as shown in Fig. 5, quantication
-MoO3 sample. In numerical analysis terms, this means that for of the percent area contribution of each component as a function
these data the spectral differences approach the differences due to of X-ray exposure time was done for both data subsets, MoO2 and
noise. Hence to evaluate the more subtle changes in MoO2 due to -MoO3 . The MoO2 sample showed a decrease over time of the Mo
X-ray exposure shown in Fig. 2A, it was assumed that the -MoO3 (VI) contribution coupled to an increase of the Mo (V) contribution,
XPS spectra components in the MoO2 spectra can be modeled using whereas the Mo (IV) contribution remained steady. In the case of
the spectral forms v4 -Mo (V) and v4 -Mo (VI) computed above for the -MoO3 sample, similar trends were observed for Mo (VI) and
the -MoO3 sample (Fig. 3B). Mo (V). These variations in the MoO3 and MoO2 samples suggested
Fig. 4 illustrates how the spectral forms Mo (V) (black line) and that changes in both samples induced by the X-ray exposure during
Mo (VI) (blue line), derived from the -MoO3 data set, were used to the measurements was associated with MoO3 , while the X-rays had
estimate spectral components nominally assigned to MoO2 signal no effect on the MoO2 sample.
J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161 157

Fig. 4. Construction of a XPS model for a Mo 3d spectrum of the MoO2 data set. (A)
A synthetic line shape, overlaid over the experimentally obtained Mo 3d spectrum,
formed by rst imposing the v4 -Mo (V) and v4 -Mo (VI) components derived from
the model for the MoO3 crystalline sample, then determining four peaks for Mo 3d5/2
(green LF line shapes 1, 2, 3, 4) and four merged peaks for Mo 3d3/2 (unnumbered
green line) sufcient to accommodate intensity not accounted for by the v4 -Mo (V)
and v4 -Mo (VI) components, and (B) the same model as in (A) where the synthetic
LF components were summed to form a single complex line shape (green) once a
consistent model with the experimental data emerged. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of
the article.)

quantitatively observed and as shown in Fig. 6, the lowest bind-


ing energy Mo 3d doublet (Mo (IV)), having a Mo 3d5/2 component
at 230.5 eV, increased in intensity/percent area contribution as
the deposition potential was increasingly negative. The resulting
Fig. 3. (A) Diagram showing the numerical procedure followed to compute 2D vec-
tors (spectral forms) v3 and v4 , and (B) spectral forms v1 , v2 , v3 and v4 showing Mo
spectral envelope, however, was very complex and could possibly
3d, O 1s, C 1s, Mo 4p and valence band energy regions. The spectral components v2 contain many oxidation states. This has been previously observed
(black line) and v1 (blue line) used to compute v3 and v4 are shown in B.5. The for amorphous molybdenum oxides and attributed to the presence
spectral form v4 was constructed with the intention of creating a spectral compo- of oxygen vacancies [35].
nent Mo (VI). (C) Spectral components v4 -Mo (V) and v4 -Mo (VI) tting a spectrum
Next, the amorphous molybdenum oxide lm electrodeposited
of the MO3SS. (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of the article.) at 0.9 V (P3-2) was subjected to X-ray exposure to induce sys-
tematic changes. Fig. 7 shows subtle differences in the Mo 3d XPS
spectra (tted using the IASM) resulting from the speciation of
3.3. XPS analysis of the amorphous molybdenum oxide samples the sample caused by the invasive X-ray probe. Fig. 8 shows the
percent area contributions of the Mo (VI), Mo (V) and Mo (IV) spec-
Amorphous molybdenum oxide samples were electrodeposited tral components along with atomic concentrations of the C 1s and
at increasingly negative potentials: 0.7 V (P3-1), 0.9 V (P3-2) and O 1s orbitals as function of X-ray exposure time. The Mo (V) con-
1.1 V (P3-3). XPS was performed on each sample and then ana- tribution increased during the exposure from 20% to 28% while the
lyzed using the XPS models previously constructed for the -MoO3 contribution of Mo (VI) decreased from 10% to 7.5%. This coincided
and MoO2 samples. The Mo 3d spectra of samples P3-1, P3-2 and with a decrease in C 1s and O 1s percent atomic concentrations. The
P3-3 and the tting models are shown in Fig. 6. Each spectrum was surface sensitive nature of XPS may explain the Mo (V) component
tted by rst imposing the v4 -Mo (V) and v4 -Mo (VI) components growth with exposure time resulting from the loss of a carbon and
derived from the model for the -MoO3 crystalline sample shown oxygen contamination overlayer. While this XPS doublet compo-
in Fig. 3B, and then adding a third Mo 3d doublet attributed to a nent was assigned to Mo (V), the true meaning for that component
Mo (IV) component and constrained in terms of relative intensity was not clear. We speculate that this component might correspond
3:2 due to the spinorbit splitting. We named this tting model the to a non-stoichiometric molybdenum oxides called Magneli phases
informed amorphous sample model (IASM), as it incorporates com- Mon O3n 1 resulting from the reduction of bulk molybdenum tri-
ponents informative of the sample degradation process previously oxide [48,49]. The assignment of these broad peaks to Mo 3d (V)
studied. was therefore seen as the mean component representing a broad
According to the Pourbaix diagram [47], an increasingly negative range of Magneli phases.
deposition potentials should result in more reduced molybdenum One outstanding question is the relationship of amorphous Mo
species present in the sample. This indeed was qualitatively and oxide assigned to Mo (IV) in Fig. 6 and the MoO2 crystalline spectra
158 J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161

Fig. 6. Mo 3d spectra of amorphous samples P3-1, P3-2 and P3-3 electrodeposited


at 0.7 V, 0.9 V and 1.1 V, respectively, and tted using the IASM.

using synthetic line shapes to create pairs of peaks representing


a doublet where the only constrain was a peak intensity ratio 3:2
due to spinorbit splitting. It is evident in Fig. 9 that the differ-
ent models IASM and PSM, applied to the same Mo 3d spectrum
led to very different relative proportions of intensity attributed to
different oxidation states. We do not consider the PSM to be a true
representation for the oxidation states in the amorphous sample, as
it is intentionally poorly constrained in order to illustrate a number
of points:

Fig. 5. Percent area contribution of XPS components attributed to Mo (IV), tenta-


tively Mo (V) and Mo (VI) species as a function of X-ray exposure time of (A) MoO2
and (B) -MoO3 samples as determined applying the models in Figs. Fig. 44B and
Fig. 33B, respectively.

in Fig. 4. The peak separation between the Mo (VI) and Mo (IV)


is signicantly different between amorphous (1.9 eV) and crys-
talline (3.5 eV) oxides. Further, the amorphous oxide in Mo (IV)
state appear to only require a simple doublet to account for the sig-
nal not allocated to Mo (VI) and Mo (V), while crystalline Mo (IV) is
more complicated than a single doublet pair. While multi-factorial
in origin, these differences are possibly explained by the different
atomic separation between amorphous and crystalline materials
resulting in variations in potential experienced by core level Mo 3d
electrons from essentially the same nominal material [50].

3.4. Comparison between the different methods to analyze XPS


spectra of molybdenum oxide

XPS spectra from the amorphous molybdenum oxide samples


were analyzed using the XPS tting model proposed in this work
(IASM), and for comparison, a synthetic model built using binding
energies assignments available in the literature [34], here called
purely synthetic model (PSM). Fig. 9A shows a typical Mo 3d spec-
trum of an amorphous molybdenum oxide sample tted using the Fig. 7. Mo 3d spectra of the amorphous sample P3-2 obtained at different X-ray
IASM (see Section 3.3). The PSM, shown in Fig. 9B, was constructed exposure times (min), in the text next to each spectrum, and tted using the IASM.
J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161 159

as part of the trial and error process via adjustments made to


parameter constrains and line shape parameters which involve a
decision process where unacceptable relationships are rejected,
while those deemed plausible are progressively incorporated
into the model construction. There is an underlying assumption
that the number of doublet peaks required to understand the
spectral shape is known. The greatest cause for concern when
measuring the peak intensities in Fig. 9B was the selection of the
three doublet peaks. A secondary concern is the imposition of
constraints for the FWHM as these alone can greatly inuence
the outcome for an optimization algorithm [52].
3. Arbitrariness involved in choosing line shape types. The line
shapes are also very inuential in the outcome in terms of rel-
ative peak intensities and are therefore an important choice
when tting a data envelope. In the PSM model, a LF line shape
for Mo (VI) and Mo (V) species was selected due to the com-
monly accepted Gaussian instrumental broadening in addition
to the Lorentzian energy distribution of the electrons [52]. Fur-
Fig. 8. Percent area contribution of XPS spectra components attributed to Mo (IV), ther, asymmetry within a line shape for the Mo (IV) peaks may
tentatively Mo (V) and Mo (VI) species along with percent atomic concentration of be required [29]. Without much guidance from the data for the
O 1s and C 1s orbitals as function of X-ray exposure time of the amorphous sample selection of the asymmetry parameters, it is extremely difcult
P3-2. The data points were obtained by tting each spectra using the IASM.
to make a choice that would be signicant to the outcome.
4. Guidance required to do changes to a model when applying
to other similar data. The PSM model cannot be applied with-
1. Uncertainties due to noise. While the data reproduction is good out modications to another similar spectrum, where similar
as measured by the residual standard deviation (a value close to components are expected. For this reason, this model is said
unity), the model was susceptible to noise as illustrated by the to be ad hoc in nature. The ability of the model to t a sim-
estimated uncertainties in the % area parameter in Fig. 9B cal- ilar spectrum requires changes to FWHM and binding energy
culated using a Monte Carlo method [51]. The peaks assigned shifts of particular components. These adjustments to a model
to Mo (IV) potentially implied an error as large as 8%, from the must be explained in some manner to scientically justify such
repeatability perspective, while the intensity for the Mo (VI) dou- alterations.
blet could be expected to differ by 22% simply due to measuring
the same sample on other occasions.
2. Arbitrariness involved in choosing line shape parameters In conclusion, a consequence of doing XPS tting without using
and contributing spectral components. When constructing a appropriate guidance about the structural, physical and chemi-
model, such as the PSM in Fig. 9B, a Monte Carlo method is used cal processes affecting the sample leads to meaningless subjective

Fig. 9. Two XPS tting models for a Mo 3d spectrum of an amorphous molybdenum oxide sample: (A) IASM, and (B) PSM.
160 J. Baltrusaitis et al. / Applied Surface Science 326 (2015) 151161

data interpretation and quantication, while still obtaining plau- [11] B. Mendoza-Snchez, T. Brousse, C. Ramirez-Castro, V. Nicolosi, P.S. Grant, An
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