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Systematic XPS studies of metal oxides, hydroxides and peroxides

Jean-Charles Dupin,a Danielle Gonbeau,*a Philippe Vinatierb and Alain Levasseurb

a L aboratoire de Physico-Chimie Mole culaire-UMR CNRS 5624, He lioparc Pau-Pyre ne es, 2 Av.
du Pre sident Angot, 64053 Pau Cedex 9, France
b Ecole Nationale Supe rieure de Chimie et Physique de Bordeaux, Avenue Pey Berland, B.P. 108,
33402 T alence Cedex, France

Received 4th November 1999, Accepted 10th January 2000

The results of a systematic XPS study, under high controlled conditions, of di†erent basic oxides of transition
Published on 21 February 2000 on http://pubs.rsc.org | doi:10.1039/A908800H

metals, alkali and alkaline-earth metals are presented ; the XPS data of some hydroxides and peroxides are also
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reported. Variations of the O 1s binding energies are analysed and one point of interest is the large binding
energy scale obtained for O 1s peaks all associated with a ““ 2 [ ÏÏ formal charge. Through extended HuŽckel
theory-tight binding (EHT-TB) calculations, attempts are made to rationalize the observed variations. The
results illustrate the signiÐcant di†erences between real charges on oxygen atoms in transition metal and
alkaline-earth oxides.

Introduction
Oxides comprise a very diverse class of compounds with
properties covering almost all aspects of material science and
physics.1 They Ðnd applications in many Ðelds of technical
interest from nonlinear optics to sensors and catalysis.
During the last few years various researchers have dealt
with the characterization of basic oxides with catalytic or con-
ductivity properties using XPS.
Transition metal oxides have been intensively investigated
as layers grown in situ on the corresponding metal or poly-
crystalline systems.2h51 Although most studies were mainly
focused on the binding energy of metal atoms, only some
papers have been devoted to detailed analyses of the O 1s
spectrum.39,51 Very few interesting XPS data have been
reported for the O 1s peak of alkali and alkaline-earth
oxides.52h56 The difficulties in obtaining reliable O 1s data are
related to hydroxylation and/or carbonation phenomena.
Indeed, metal oxides may undergo hydroxylation and/or car-
bonation when exposed to air, a phenomenon which may
progress into the bulk to a di†erent extent depending on the
material and on the aging time. Typical cases of total
hydroxylation/carbonation are the oxides of basic cations
such as alkali or alkaline-earth metals where, after long expo-
sure, the whole oxide material can be degraded.
In this work we have examined by XPS di†erent basic
oxides of transition metals, alkali and alkaline-earth metals
and also some hydroxides and peroxides. Our major objective
was to obtain, under controlled conditions, a large scale of
comparable binding energies for the O 1s peak. In relation to
the variations of electronic structure, we have undertaken the
characterization of the di†erent species of ““ O2~ ÏÏ ions in these
metal oxides ; some of these experimental results are supported
by periodical calculations [extended HuŽckel theory-tight
binding (EHT-TB) method].
Experimental and theoretical conditions
Experimental conditions
The XPS analyses were performed with a Surface Sciences
Instruments spectrometer (model 301) using a focused mono-
chromatized Al-Ka radiation (1486.6 eV). The diameter of the
DOI : 10.1039/a908800h
This journal is ( The Owner Societies 2000
irradiated area was 600 lm and the residual pressure inside
the analysis chamber was in the 10~8 Pa range. The spectro-
meter was calibrated by using the photoemission lines of Au
(Au 4f \ 83.9 eV, with reference to the Fermi level) and Cu
7@2
(Cu 2p \ 932.5 eV) ; for the Au 4f line, the full width at
3@2 7@2
half maximum (FWHM) was 0.86 eV under the recording con-
ditions. Peaks were recorded with a constant pass energy of 50
eV.
As the question of experimental conditions is central, high
purity samples were Ðxed on the sample holder in a glove box
Ðlled with a continuous ultrahigh purity N atmosphere (O
2 2
and H O below 2 and 7 ppm respectively) and directly Ðxed
2
onto the introduction chamber of the spectrometer. The
powders were analysed before and after a Ðne grinding in the
glove box. In order to precisely make some assignments, a few
XPS experiments were also performed after taking the
samples out the glove-box.
Charging e†ects were minimized with a low energy electron
Ñood gun in conjunction with a transmitting Ðne mesh prox-
imity screen. The calibration of binding energy scale was per-
formed with the C 1s line (284.6 eV) from the carbon
contamination layer.
The XPS signals were analysed by using a peak synthesis
program in which a nonlinear background is assumed57 and
the Ðtting peaks of the experimental curve are deÐned by a
combination of gaussian (80%) and lorentzian (20%) distribu-
tions.
Extended HuŽ ckel theory-tight binding (EHT-TB) calculations58
The parameters generally used in the non-periodic extended
HuŽckel method have been chosen for each atom.58 The cell
parameters used for the calculations are shown in Table 1.
The routine of k points automatic generation associated
with the calculation program allows a regular network of the
irreducible Brillouin zone to be obtained, taking into account
the symmetry of the whole crystal.
Results
Transition metal oxides
XPS results obtained for transition metal oxides (TM) (TiO ,
2
ZrO , Nb O , MoO , WO , CoO, Co O , NiO, ZnO) are
2 2 5 3 3 3 4
Phys. Chem. Chem. Phys., 2000, 2, 1319È1324 1319
 View Online
Table 1 Cell parameters

TiO (quadratic)59 a \ b \ 4.594 AŽ ; c \ 2.958 AŽ

ZrO2 (monoclinic)60 a \ 5.145 AŽ ; b \ 5.207 AŽ ; c \ 5.311 AŽ ; b \ 99.23¡
2
MoO (orthorhombic)61 a \ 3.92 AŽ ; b \ 13.94 AŽ ; c \ 3.66 AŽ
WO 3(monoclinic)62 a \ 7.297 AŽ ; b \ 7.539 AŽ ; c \ 7.688 AŽ ; b \ 90.91¡
3
CoO (cubic)63 a \ 4.2667 AŽ
NiO (cubic)63 a \ 4.1684 AŽ
CaO (cubic)63 a \ 4.8105 AŽ
SrO (cubic)63 a \ 5.1602 AŽ

reported in Table 2 and some O 1s spectra are presented in
Fig. 1.
In all cases an intense peak is observed at around 530 eV,
slightly higher for MoO and WO (D530.5 eV), slightly
3 3
lower for CoO, NiO, Co O (D529.5 eV). It is a single peak
3 4
for WO and the main component for the other compounds :
3 2
it is attributed to the ““ O2~ ÏÏ anions of the crystalline network.
These results agree with the data reported in the liter-
Published on 21 February 2000 on http://pubs.rsc.org | doi:10.1039/A908800H
The assumption of di†erent valence states for the metal23 or
several Ðnal states64 has been made, but in most cases this
structure has been assigned to contamination surface species.
The adsorption of OH~ or CO 2~ groups was suggested in
3
comparison with the binding energy of the O 1s peak in
hydroxide or carbonate compounds [Ni(OH) , Co(OH) or
2
Ni(CO )30] ; other adsorbed species such as ““ O 2~ÏÏ were also
3 2
proposed. Di†erent thermic or ionic etching treatments were

ature.10,15h17,19,22,23,27,28,30,32,38,40,41,43,45,47,48,50,51 realized in order to support these di†erent hypothesis.36

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Beside this peak, a second component can be observed However, conÑicting results were obtained and the sole possi-
(except for WO ) in the range 531.1È531.9 eV ; its intensity is bility of contamination surface species was ruled out in several
3
about 20% relative to the main peak, except for MoO . cases. Jimenez et al.50 attribute the lateral peaks observed in
3
These lateral structures have been reported in many studies, cobalt oxides to low coordinated oxygen ions at the surface of
but they are not precisely attributed. Only some studies have the samples. It was also suggested22 that an oxygen partial
been devoted to detailed analyses especially in the case of integration might occur in the bulk and generate a high
cobalt and nickel oxide. binding energy component, more or less intense, for the O 1s
peak. In a mixed chemisorptionÈpenetration situation, bond
Table 2 XPS results for the transition metal oxides examined : lengths and crystal potentials may vary signiÐcantly leading to
binding energies (eV) ; (full width at half maximum) ; relative percent- a range of O 1s binding energies (BEs) ; this may also account
ages for the large width and variable BE positions of the lateral
structure.
Compound
Although the aim of this work is not centered on this lateral
0 1s Ti 2p structure, it is worth noting that we have observed : (i) for
3@2h1@2
TiO 530.0 (1.6) 87% 458.7È464.4 cobalt and nickel oxides a higher intensity of this component
2
rutile 531.8 (2.0) 13% (1.5) (2.2) compared to that of other compounds ; (ii) for molybdenum
O 1s Zn 2p and tungsten oxides a low intensity or the absence of this
3@2h1@2
ZrO
2
530.1 (1.4) 78% 332.8È346.4 component ; and (iii) for all the transition metal oxides, an
531.6 (1.7) 22% (2.7) (2.8)
O 1s Nb 3p
3@2h1@2
HÈNb O 530.0 (1.5) 86% 365.1È380.6
2 5
531.4 (1.7) 14% (3.0) (3.2)
O 1s Mo 3d
5@2h3@2
MoO 530.6 (1.3) 94% 232.6È235.8
3
532.0 (1.3) 6% (1.2) (1.2)
O 1s W 4f
7@2h5@2
WO 530.6 (1.4) 35.7È37.9
3
(1.2) (1.2)
O 1s Co 2p
3@2h1@2
CoO 529.5 (1.6) 60% 779.9È796.1 71%
531.2 (2) 40% (4.5) (4.2)
796.1a [0.30] 802.3a [0.64] 29%
(4.5) (4.2)
O 1s Co 2p
3@2h1@2
Co O 529.5 (1.3) 72% 779.5È794.5 55%
3 4
531.1 (1.9) 28% (1.9) (1.9)
788.9a [0.15]È804.1a [0.31] 11%
(3.5) (3.5)
781.1È796.1 34%
(2.5) (2.5)
O 1s Ni 2p
3@2h1@2
NiO 529.5 (1.2) 70% 853.9È871.9 26%
531.1 (1.5) 30% (1.8) (2.0)
860.9a [1.6]È879a [2.1] 46%
(5.0) (5.0)
855.8È873.8 28%
(2.4) (2.5)
O 1s Zn 2p
3@2h1@2
ZnO 530.1 (1.3) 77% 102.1È104.4
531.6 (1.6) 23% (1.8) (1.9)
a Satellite peak (secondary ionization) ; [I satellite peak/I main peak]. Fig. 1 O ls peaks of polycrystalline TM oxides : (a) TiO ; (b) MoO ;
2 3
(c) WO ; and (d) ZnO.
3
1320 Phys. Chem. Chem. Phys., 2000, 2, 1319È1324
 View Online
enhanced intensity of this lateral structure after exposure to Table 3 XPS results for the alkali and alkaline-earth oxides, hydrox-
atmosphere ; a grinding in the glove box leads to a decrease of ides and peroxides examined ; binding energies (eV) ; (full width at half
maximum) ; relative percentages
this component and to its total disappearance in the case of
WO ; in addition it is to be noted that a peak develops at Oxides
3
higher air exposures around 532.5 eV.
The analyses on transition metal oxides have shown the fol- O 1s Ca 2p
3@2h1@2
lowing peaks : (i) in the 529.5È530.5 eV range, O 1s peaks CaO 528.5 19% 345.4È348.9 40%
(1.2) (1.5) (1.5)
characteristic of the ““ O2~ ÏÏ ions of the crystalline network ;
530.8 81% 346.4È350.0 60%
and (ii) in the 531È532 eV range, O 1s lateral structures of (1.7) (1.6) (1.6)
variable intensityÈalthough a precise assignment is not pos-
O 1s Sr 3d
sible it seems reasonable to consider ionizations of weakly SrO 527.7 15% 5@2h3@2 35%
131.7È133.5
adsorbed species and also ionizations of oxygen ions with par- (1.4) (1.4) (1.4)
ticular coordinations more speciÐcally integrated in the sub- 530.4 85% 132.7È134.4 65%
surface (bulk structure near the surface). Indeed, this (1.9) (1.4) (1.4)
component is present in most cases, after grinding in the glove
Hydroxides
box. This suggests the existence in the subsurface of oxygen
ions which bear lower electron density than the ““ O2~ ÏÏ ions ; O 1s Na 1s
formally these oxide ions could be described as ““ O~ ÏÏ species. 530.3 1070.8
They can be associated with sites where the coordination NaOH (1.8) (1.8)
Published on 21 February 2000 on http://pubs.rsc.org | doi:10.1039/A908800H

number of oxygen ions is smaller than in a regular site, with a O 1s Sr 3d

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5@2h3@2
higher covalence of the MÈO bonds. A reasonable hypothesis Sr(OH) 530.5 132.8È134.5
2 (2.0) (1.6) (1.6)
is to consider the existence, in variable proportions for the
di†erent transition metal oxides of defects in the subsurface. O 1s Ca 2p
3@2h1@2
As previously noted,22,50 it is likely that this last possibility is Ca(OH) 530.8 346.3È349.8
2
(1.7) (1.8) (1.8)
especially important in the case of cobalt and nickel oxides. It
is also to be noted that, after grinding, a better stoichiometry O 1s Li ls
is obtained when this lateral structure is taken into account. Li(OH) 531.1 54.7
(2.0) (1.2)

Alkali and alkaline-earth oxides, hydroxides, peroxides Peroxides

In order to extend the scale of O 1s binding energies we have O 1s Na ls

undertaken the analysis of di†erent alkali and alkaline-earth
oxides, hydroxides and peroxides.
XPS results are reported in Table 3 and Fig. 2.
For CaO and SrO, two components, which are clearly
separated, appear at the O 1s level : CaO : 528.5 eV, 530.8 eV ;
and SrO 527.7 eV ; 530.4 eV.
The data obtained for the O 1s peak of Ca(OH) and
2
Sr(OH) lead us to assign the components at 528.5 and 527.7
2
eV to the respective oxides.
Na O 530.8 1071.1
2 2
(1.9) (2.0)
O 1s Sr 3d
5@2h3@2
SrO 531.1 132.7È134.6
2 (1.7) (1.6) (1.6)
It is to be noted that for high purity of the oxides, drying at
high temperature (D1200 K) for two days was necessary ;
under these conditions, only oxides and hydroxides were
detected, no trace of carbonates was detected (the character-
istic C 1s component at around 289.3 eV was not present).
After a very short air exposure only hydroxides, in both cases,
were identiÐed.
To our knowledge these results correspond to the Ðrst XPS
characterisation of oxide/hydroxide sequence for poly-
crystalline samples of CaO and SrO. The easy degradation of
such compounds by hydroxylation previously led to inaccu-
rate or wrong assignments.52,54 Only one study reports a
sequence for the oxides CaO and SrO that agrees with the
present results.56 In this work metal oxides were treated in the
form of Ðlms on metal surfaces at 600È650 K ; relative to our
results the small di†erence in binding energies (D0.3 eV) is
due to changes in the calibration procedure.
Our approach was less successful when applied to Li O and
2
Na O for which only hydroxides have been identiÐed.
2
In the case of the hydroxide compounds the data reported
in Table 2 show a range of O 1s BEs from about 530.3 to
531.1 eV. For the two peroxides examined (Na O and SrO )
2 2 2
slightly higher values were obtained (from 0.4 to 0.7 eV).
For the Ðrst time, the whole oxide/hydroxide and peroxide
of strontium sequence has been characterized with well di†er-
entiated binding energies : SrO 527.7 eV ; Sr(OH) 530.4 eV ;
2
and SrO 531.1 eV.
2

Discussion
Fig. 2 O ls peaks of alkaline-earth oxides, hydroxides and peroxi- The whole set of comparable binding energies obtained for the
des : (a) CaO ; (b) SrO, (c) Sr(OH) ; (d) SrO . O 1s peak (Fig. 3) deserves some comment.
2 2

Phys. Chem. Chem. Phys., 2000, 2, 1319È1324 1321

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Fig. 3 A binding energy scale for the O ls peak.

On the high binding energy side, precise assignments are alkaline-earth oxides compared to transition metal oxides.
difficult in relation to the existence of ionizations associated The signiÐcant increase of the electronic density around
with weakly adsorbed species. The analyses have shown : (i) oxygen atoms is consistent with the evolution of the binding
Published on 21 February 2000 on http://pubs.rsc.org | doi:10.1039/A908800H

from 530.5 to 531.1 eV, ionization characteristics of oxygen energies.

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species integrated in the material as OH~ or O 2~ ; and (ii)
2
from 531.1 to 532 eV, ionization of oxygen species that could
allow compensation for some deÐciencies in the subsurface of
TM oxides. Formally, these oxide ions could be described as
““ O~ ÏÏ speciesÈindeed, owing to a higher covalence of the
MÈO bonds these low coordinated oxygen ions would be
characterized by a lower electron density than the classical
““ O2~ ÏÏ ions.
In the 532È533 eV range, before grinding, peaks have been
observed ; the increasing intensity at higher air exposures and
the disappearance after grinding suggest the existence of ion-
ization associated with weakly adsorbed species.
The most interesting result of this work is concerned with
the low energy side of the O 1s binding energy scale (527.7È
530.5 eV) which corresponds to oxygen ions all associated
with a ““ 2 [ ÏÏ formal charge. Indeed, rather small variations
are observed for transition metal oxides but much more sig-
niÐcant shifts are noted for alkaline-earth oxides compared to
transition metal oxides.
It is well established that the binding energies determined
by XPS for the core electrons of an atom are dependent on
the chemical state of this atom. Di†erent relations between
chemical shifts and real charge variations such as those of a
potential model have been used successfully.65 Generally, an
increase of the negative charge on the ionized atom A leads to
a lowering of its core binding energies. On this basis empirical
correlations *E % q have been established.
b A
For the main oxides examined, the EHT-TB calculated net
charges on oxygen atoms have been reported in Table 4. The
values are in good agreement with some available data in the
literature obtained by more sophisticated calculations.66h68
Very small variations are observed for transition metal
oxides and no correlation is possible with the chemical shifts.
However, clear changes are observed for the net charges q of
0
Considering these results, it is important to note that three
factors can disturb the simple binding energyÈcharge corre-
lation *E % q : (i) the electrostatic potential due to the
b A
charge distribution on the atoms surrounding the ionized site ;
(ii) Ðnal state e†ects ; and (iii) work functions.
In fact, the data obtained for transition metal oxides show,
as previously observed for transition metal disulÐdes,69 the
limits of a simple *E % q rationalization. However, the clas-
b A
sical *E % q correlations can reveal general trends as
b A
observed for alkaline-earth oxides compared to transition
metal oxides.
In addition, according to these results it appears that the
formal oxidation numbers associated with entire charges cor-
respond to a convenient language, but actually many grada-
tions can exist. They show for oxygen ions of transition metal
oxides a real charge clearly di†erent from the ““ 2 [ ÏÏ formal
one and in comparison, a clear increase of the electronic
density for oxygen ions of alkaline-earth oxides.
In order to investigate this information more deeply, we
have undertaken DOS curve analysis for two characteristic
compounds, TiO and SrO.
2

Table 4 EHT-TB calculations : net charges on oxygen and metal

atoms

Compound q q
0 M
TiOa [1.15 ]2.3
ZrO2 [1.18 ]2.36
MoO2 [1.22 ]3.66
WO 3b [1.2 ]3.6
CoO3 [1.05 ]1.05
NiO [0.9 ]0.9
CaO [1.78 ]1.78
SrO [1.85 ]1.85
a Ref. 66 : q \ [1.3 q \ ]2.6. b Ref. 67 : q \ [1.3 q \ ]3.4 ; Fig. 4 Density of states (EHT-TB) : (a) total DOS for TiO (shaded
0
ref. 68 q \ [1.362 q \
Ti ]4.086. 0 W part projected DOS of titanium) ; and (b) total DOS for SrO2 (shaded
0 W part projected DOS of strontium).

1322 Phys. Chem. Chem. Phys., 2000, 2, 1319È1324

 View Online
In Fig. 4, we have reported the total and projected density 22 T. J. Chuang, C. R. Brundle and D. W. Rice, Surf. Sci., 1976, 59,
of states (DOS) of these two oxides over an energy window 413.
23 J. Haber, J. Stoch and L. Ungier, J. Electron. Spectrosc., 1976, 9,
corresponding to the valence zone. As expected, the two bands 459.
(around 15 and 33 eV) are mainly located respectively on the 24 M. Oku and K. Hirokawa, J. Electron. Spectrosc., 1977, 10, 103.
p and s orbitals of the ligands. In addition, examination of 25 C. N. Sayers and N. R. Armstromg, Surf. Sci., 1978, 77, 301.
Fig. 4(a) reveals a non-negligible participation of titanium 26 M. Scrocco, Chem. Phys. L ett., 1979, 61, 453.
(mainly d orbitals) in the two bands which is evidence of e†ec- 27 C. N. R. Rao, D. D. Sarma, S. Vasudevan and M. S. Hegde, Proc.
tive metalÈligand interactions ; for SrO clearly less important R. Soc. L ondon, Ser. A, 1979, 367, 239.
interactions occur between strontium orbitals (mainly s 28 G. Hollinger, V ide Couches Minces, 1980, 201, 405.
29 H. Chermette, P. Pertosa and F. M. Michel-Calendini, Chem.
orbitals) and orbitals (s and p) of oxygen atoms. These results
Phys. L ett., 1980, 69, 240.
are consistent with signiÐcant charge-transfers O ] M in the 30 M. W. Roberts and R. S. C. Smart, Chem. Phys. L ett., 1980, 69,
case of transition metal oxides, weaker charge transfer for 234.
alkaline-earth oxides and consequently for more negative 31 D. D. Sarma and C. N. R. Rao, J. Electron. Spectrosc., 1980, 20,
oxygen atoms in these last materials. 25.
32 S. Cochran and F. P. Larkins, J. Chem. Soc., Faraday T rans.,
1985, 81, 2179.
33 C. Ocal and S. Ferrer, Surf. Sci., 1987, 191, 147.
34 G. Munuera, A. R. Gonzalez-Elipe, J. P. Espinos and A. Navio,
Conclusions Mater. Sci., 1988, 25/26, 467.
35 M. E. Levin, M. Salmeron, A. T. Bell and G. A. Somorjai, Surf.
Through XPS analysis, under highly controlled conditions, of
Published on 21 February 2000 on http://pubs.rsc.org | doi:10.1039/A908800H

Sci., 1988, 195, 429.

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several transition metals, alkali and alkaline-earth oxides,
hydroxides and peroxides, a large scale of comparable binding
energies has been obtained for the O 1s peak.
This study has allowed the characterization of some new
XPS data especially the whole oxide, hydroxide and peroxide
sequence in the case of strontium.
In addition, these results are important as reference data for
the analysis of amorphous compounds for which unusual
coordinations of oxygen ions may exist with changes in the
covalent character of MÈO bonds compared to classical ones.
One point of interest is also the large binding energy scale
(D3 eV) obtained for O 1s peaks all associated with a ““ 2 [ ÏÏ
formal charge. Although variations of EHT-TB net charges
have shown the limits of the classical *E % q correlation for
b A
transition metal oxides, they are consistent with the general
shift observed from transition metal oxides to alkaline-earth
oxides. These results illustrate the signiÐcant di†erence
between real charges on oxygen atoms in transition metal and
alkaline-earth oxides.
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