Introduction to XPS Studies of Metal

and Metal-oxide Nanosystems

Lidia Armelao, Davide Barreca, Gregorio Bottaro, and Silvia Gross
ISTM-CNR and INSTM, Department of Chemistry, University of Padova, Via Marzolo, 1-35131,
Padova, Italy

Alberto Gasparotto, Cinzia Maragno, Eugenio Tondello, and Andrea Zattin

Department of Chemistry, University of Padova and INSTM-Via Marzolo, 1-35131 Padova, Italy

共Received 19 January 2005; accepted 8 February 2005; published 8 March 2005兲

Metal and metal-oxide based nanosystems are intriguing candidates for a plethora of advanced
applications thanks to their diversified chemico-physical properties, that can be further tailored by
the use of proper synthesis procedures. Among the different preparation techniques, chemical vapor
deposition 共CVD兲, rf sputtering, and sol-gel 共SG兲 display promising features for the design and
control of nanosystem characteristics even beyond thermodynamical predictions, thanks to the soft
synthetic conditions that enable nucleation to prevail over the subsequent particle agglomeration. In
this context, a direct feedback between the nanosystem synthesis and characterization represents a
unique tool for the optimization of the process. In particular, XPS spectroscopy plays an outstanding
role for the investigation of surface and in-depth chemical composition of thin films as a function
of the experimental conditions. In this article, the attention is devoted to the XPS analysis of
different kinds of nanosystems, from nanostructured thin films (LaCoO3) to oxide clusters in silica
matrices 共HfO2 and HfO2 –ZrO2 in SiO2) and metal cluster-based composites 共Au/graphite,
Au/TiO2 , Ag/SiO2). This Introduction provides an overview of the data presented in the collected
spectral data records, focusing in particular on the interest in these systems and on the most relevant
results obtained by XPS investigations. © 2005 American Vacuum Society.
关DOI: 10.1116/11.20050199兴

Keywords: Metal-oxide nanosystems; CVD; Sol-Gel; rf sputtering; XPS

PACS: 61.46.⫹w, 79.60.Jv, 81.15.Gh, 81.20 Fw, 81.15.Cd

OVERVIEW
Oxide-based materials show a broad spectrum of optical,
catalytic, magnetic, and electrical properties 共Ref. 1兲, owing
to their different structures and chemico-physical character-
istics. This variety discloses interesting perspectives for the
design and the preparation of innovative functional systems,
also thanks to the possibility of controlling their organization
on the nano-dimensional scale 共1–100 nm兲 共Ref. 2兲. In fact,
this size domain implies a much larger surface-to-volume
ratio, together with an enhanced chemical reactivity, with
respect to conventional materials 共Refs. 3 and 4兲. As the size
of the ‘‘building blocks’’ decreases, a progressive transition
from bulk to molecular properties occurs, which is related to
quantum confinement or more generally to restricted geom-
etry 共Refs. 5 and 6兲. Besides nanostructured thin films, com-
posites based on metal and oxide nanoparticles in/on suitable
matrices have drawn a remarkable attention, due to the pos-
sibility of tailoring their properties as a function of particle
dimension and distribution 共Refs. 2, 7, and 8兲. These size
effects are of notable importance in the fields of catalysis, gas
sensing, photonics, and energetics 共Ref. 9兲, where the func-
tional performances are further influenced by different fea-
tures, i.e., phase composition, structure, morphology, and de-
fect content.
To this aim, an open challenge in the field of nanotech-
a兲
Author to whom correspondence should be addressed; electronic mail:
davide@chin.unipd.it
nology is the development of suitable preparative approaches
to tailor the material properties on the nanometric scale
共Refs. 10–12兲. Among the synthetic methods, CVD, rf sput-
tering and SG are some of the most relevant for their inherent
versatility 共Refs. 13–15兲. These bottom-up techniques and
their combinations provide a powerful tool for the production
of nanosystems thanks to the possibility of operating under
controlled conditions, where nucleation is favored with re-
spect to the subsequent particle growth. This feature is a
valuable tool for the control of grain size and distribution,
thus enabling the preparation of metastable phases and sys-
tems that are hardly attainable by other preparation routes.
Beyond the synthetic approach, a key step in the develop-
ment of functional nano-devices is the characterization of
their compositional and microstructural features. Particularly
critical is the surface and in-depth distribution of the different
chemical species, since the formation of interfaces, as well as
the occurrence of segregation phenomena, can be highly det-
rimental for many technological applications. In this frame-
work, the availability of analytical methods capable of thor-
oughly investigating these materials and of carrying out
reliable depth profile analysis in the nm-␮ range is an essen-
tial requirement. In this framework, XPS represents a pow-
erful method to study the chemical composition of the ob-
tained nanosystems, with particular regard to the chemical
state of the species and its dependence on the synthetic pa-
rameters.
The present volume contains a collection of our recent

Surface Science Spectra, Vol. 10, 2003 1055-5269/2003/10/137/6/$18.00 © 2005 American Vacuum Society 137

FIG. 1. Schematic representation of metal and metal-oxide nanosystems
investigated in this topic and related applications.
XPS studies on metal and metal-oxide nanosystems
approached by CVD, rf sputtering, and SG routes. Attention
is focused on representative systems 共Fig. 1兲 belonging to
the following categories:
共1兲 Oxide-based nanostructured thin films (LaCoO3)
obtained by an innovative hybrid CVD/SG approach
共Refs. 16 and 17兲;
共2兲 oxide clusters in silica matrices (HfO2 and HfO2 –
ZrO2 in SiO2) obtained by SG processes 共Ref. 18兲;
共3兲 metal cluster-containing composites 共Au/HOPG
where HOPG⫽highly oriented pyrolitic graphite, Au/TiO2
and Ag/SiO2), synthesized by rf sputtering and combined rf
sputtering/SG routes 共Refs. 19–21兲.
The trait-de-union in the nanosystem characterization is
represented by XPS spectroscopy, which enables to evi-
dence important interrelations between system properties
and processing conditions. In particular, XPS was profitably
exploited to get information concerning: 共1兲 the elemental
percentages and metal oxidation states; 共2兲 the nature of the
present chemical moieties and the intermixing of the spe-
cies, which can lead to the formation of solid solutions; 共3兲
the in-depth elemental distribution. To this regard, informa-
tion provided by XPS was integrated and extended by sec-
ondary ion mass spectrometry 共SIMS兲 analyses, endowed
with a higher sensitivity at low atomic concentrations with
respect to XPS.
In the present survey, we will briefly introduce the most
relevant issues regarding the chemical and physical proper-
ties of the investigated systems and their dependence on the
particular preparation route. A detailed discussion on their
XPS spectral features will be presented in the relative
papers.
OXIDE-BASED NANOSTRUCTURED THIN FILMS
LaCoO3 nanosystems are receiving increasing attention
for the development of innovative fuel cells and heteroge-
neous catalysts 共Refs. 16 and 17兲. The possibility of obtain-
ing nanophasic layers of defective LaCoO3 with controlled
138 Surface Science Spectra, Vol. 10, 2003
FIG. 2. XPS depth profile of a nanostructured LaCoO3 thin film annealed
in air at 700 °C, 120⬘ (Ar⫹ sputtering at 3.0 kV, Ar partial pressure
⫽5⫻10⫺8 mbar; rastered area ⫽2⫻2 mm2).
composition, structure, and morphology plays an important
role in these applications. In the present investigation, the
synthesis of nanostructured LaCoO3 thin films was carried
out by means of an innovative hybrid CVD/SG approach.
The adopted strategy consisted in the CVD of a La-O-based
layer on a SG cobalt oxide xerogel 关 CoOx 共OH兲y ] at tem-
peratures as low as 200 °C and in the subsequent thermal
treatment in air 共400– 800 °C, 60– 480⬘兲 共Ref. 17兲. In this
context, particular attention was devoted to achieving an
intimate La/Co intermixing already in the as-prepared sys-
tems, in order to favor reactions yielding a single La–Co–O
phase with uniform composition.
The obtained results highlighted the formation of pure
and structurally homogeneous LaCoO3 nanosystems after
annealing at 700 °C for 120⬘. XPS analyses 共Ref. 22兲
yielded valuable information concerning the surface chemi-
cal composition and metal oxidation states. In particular, the
surface O 1s peak could be fitted by three components re-
lated to lattice oxygen 共BE⫽528.8 eV兲, adsorbed oxygen
共BE⫽530.6 eV兲, and hydroxyl groups 共BE⫽531.7 eV兲. For
specimens annealed at 700 °C, the formation of LaCoO3
was confirmed by the following data: 共a兲 the La 3d signal
shape and position 关 BE共La3d 5/2 )⫽834.2 and 837.7 eV兴
agreed to a good extent with LaCoO3 values; 共b兲 the Co
2p 3/2 band was located at BE⫽779.9 eV and displayed no
shake-up satellites, thus indicating the absence of signifi-
cant Co共II兲 percentages; 共c兲 the Co Auger parameter
关␣Co⫽BE共Co 2p3/2兲⫹KE共Co LMM兲⫽1552.8 eV兴 was in
very good agreement with the LaCoO3 one 共Refs. 17
and 22兲.
Interesting results were also obtained by analyzing the
in-depth species distribution. The corresponding XPS depth
profile 共Fig. 2兲 revealed an La/Co atomic ratio very close to
1 throughout film thickness, thus showing an homogeneous
composition, free from phase segregations. Furthermore, no
carbon traces were ever detected in the inner sample layers.
These observations, together with SIMS and x-ray diffrac-
tion 共XRD兲 analyses 共Ref. 17兲, unambiguously confirmed
Introduction to XPS Studies
 FIG. 3. XPS surveys of a HfO2 :SiO2 sample, as-prepared and annealed at 800 °C for 180⬘.
the presence of pure LaCoO3 and excluded the presence of
other phases in appreciable amounts.
The present results provide evidence that good quality
LaCoO3 nanosystems can be obtained by the proposed hy-
brid approach. Nevertheless, their thermal stability range
was limited, since annealing at 800 °C produced the decom-
position of lanthanum cobaltite crystallites. To this regard,
further studies are in progress to improve the system stabil-
ity, a major requirement for their successful integration in
chemical sensor devices or thin-film fuel cell stacks.
OXIDE CLUSTERS IN SILICA MATRICES
The rapidly decreasing size of standard complementary
metal–oxide semiconductor 共CMOS兲 devices requires the
development of alternative high-␬ dielectrics as gate mate-
rials to replace silica-based technology for future advances
in microelectronics 共Ref. 23兲. Up to now, SiO2 has been
almost exclusively used on chip as dielectric interlayer
thanks to its good loss factor, thermal stability and easy
physical processing, but several oxides are currently being
investigated as substitutes for silica 共Ref. 24兲. Among
the different candidates, ZSO (ZrO2:SiO2) and HSO
(HfO2:SiO2) binary oxide mixtures have gained increasing
interest due to their stability in contact with silicon 共Refs.
25–27兲. Zirconia-silica glasses have also been investigated
as structural materials thanks to their low thermal expan-
sion, high fracture toughness and excellent chemical resis-
tance. Furthermore, mixed zirconia-silica and hafnia-silica
materials are suitable candidates for a wide spectrum of
technological applications, for instance in the field of ca-
talysis, as catalyst supports or in optics.
Different synthesis routes, ranging from chemical solu-
tion deposition 共Ref. 28兲 to ultrahigh vacuum molecular
beam epitaxy and conventional alkoxidic SG processes
共Refs. 29 and 30兲, have been used to prepare these mixed
oxide thin films.
In this study, XPS was used to characterize the surface
and in-depth composition of two different mixed oxide-
based nanosystems, namely HfO2 :SiO2 and HfO2 –ZrO2:
SiO2 thin films prepared by a modified SG procedure,
which has already been described 共Ref. 18兲.
Surface Science Spectra, Vol. 10, 2003
As regards hafnium oxide-based systems, a sample char-
acterized by a Si:Hf molar ratio of 11:1 was analyzed both
as-prepared and after thermal treatment in air at 800 °C for
180⬘ 共Ref. 31兲.
In Fig. 3, the survey spectra of the surface of the as-
prepared and annealed samples are superimposed. Both
spectra are characterized by the presence of hafnium, sili-
con, and oxygen peaks. The most remarkable difference
was the intensity of the carbon signal, which underwent an
appreciable decrease after annealing. In the latter case, both
Si 2p and O 1s peaks were symmetric and did not show the
presence of additional components. As far as oxygen is
concerned, the O 1s peak was centered at BE⫽532.9 eV, in
good agreement with the literature value for silicon dioxide
共Ref. 32兲. The Hf 4f BE was 19.0 eV, a value higher than
that reported for bulk hafnium oxide, i.e., 16.7 eV 共Ref. 32兲.
This finding could be justified by considering that, in a
system consisting of HfO2 particles dispersed in a SiO2
matrix, hafnium experiences a chemical environment which
is remarkably different from that in bulk HfO2. In a similar
way, as reported by Moon et al. 共Ref. 34兲, in a zirconia-
silica binary nanocomposite characterized by a zirconia
loading of 9.3 % wt, a shift to higher BE values of the Zr 3d
peak was detected and ascribed to the smaller relaxation
energy for highly dispersed zirconium oxide particles in
comparison with powdered ZrO2 .
In-depth profile analysis of the films revealed an even
distribution of the hafnium host species in the silica guest
matrix, irrespective of thermal treatment. In this specimen,
the average atomic percentages obtained by quantitative
analysis 共3.6% Hf, 66.7% O, 29.4% Si兲 are in very good
agreement with the nominal composition 共2.8% Hf, 66.7%
O, 30.5% Si兲.
Concerning the HfO2 – ZrO2 :SiO2 system, a sample
characterized by a Zr:Hf:Si molar ratio⫽1:1:11 was inves-
tigated before and after thermal treatment in air at 800 °C
for 180⬘ 共Ref. 35兲. The survey of the sample before and
after thermal annealing are jointly plotted in Fig. 4.
In this latter case, the measured BE of Hf 4f and Zr 3d
peaks were 18.4 eV and 183.5 eV, respectively. These val-
ues are higher than those expected in the case of pure oxides
Introduction to XPS Studies 139
 FIG. 4. XPS surveys of a HfO2-ZrO2 :SiO2 sample, as-prepared and annealed at 800 °C for 180⬘.

共Ref. 32兲, and this effect was ascribed to the mixing of guest suggesting the presence of core-level shifts due to the nano-
oxides in the host matrix. The two oxides are homoge- sized gold particles 共Ref. 36兲. The presence of carbon and
neously distributed in the silica matrix, as confirmed by oxygen contamination was limited to the sample surface.
XPS and SIMS depth profiles. On the basis of these results, a nonconventional synthetic
These findings evidence that the chosen approach is ef- approach to Au/TiO2 nanosystems was developed
fective in obtaining homogeneous dispersion of the oxides 共Ref. 20兲. The adopted technique was based on the rf sput-
in the host silica matrix, and could be profitably extended tering of gold at 60 °C on porous titania xerogels
and implemented for the preparation of further mixed oxide 关 TiOx (OH) y (OR) z 兴 obtained by SG route and on a subse-
systems homogeneous at a molecular level. quent annealing in air 共200– 600 °C, 60⬘兲 with the aim of
tailoring the Au in-depth penetration as a function of ther-
METAL CLUSTER-CONTAINING COMPOSITES mal treatment and gold content.
Gold and silver nanoparticles supported and/or embed- The above strategy enabled the synthesis of Au/TiO2
ded on/in various substrates have received an increasing nanosystems with characteristics that were strongly depen-
attention for fundamental and applicative purposes. In the dent on the deposited gold amount and processing condi-
former case, many research activities have been focused on tions. In this way, Au/TiO2 nanosystems with gold crystal
the evolution of collective properties on going from free sizes between ⬇2 and ⬇15 nm were synthesized. Annealing
atoms to nano-organized systems. In the latter, a great in- at T⭓400 °C resulted in TiO2 anatase crystallization 共⬇15
terest has been devoted to technological applications in het-
erogeneous catalysts, gas sensors, optical and optoelec-
tronic devices. The chemico-physical properties of these
composite materials are strongly dependent on the size and
shape of metal nanoparticles, as well as on metal-metal and
metal-substrate interactions. These characteristics can be
easily controlled by plasma-assisted techniques such as rf
sputtering thanks to the soft synthetic conditions and to the
competition between deposition/ablation processes charac-
terizing glow-discharges 共Refs. 9, 14, 19, and 21兲.
In this volume, the attention is initially focused on gold-
based nanosystems obtained by rf sputtering from Ar plas-
mas on HOPG at temperatures as low as 60 °C. Preliminary
scanning tunneling microscopy 共STM兲 investigations re-
vealed a homogeneous globular morphology and an en-
hanced particle agglomeration at increased deposition
times, thus highlighting a three-dimensional growth mecha-
nism 共Ref. 19兲. In this case, XPS analyses revealed the
presence of metallic Au particles and a progressive increase
of gold surface percentage with deposition time. Interest-
FIG. 5. Surface Au 4f photoelectron peak for an Au/HOPG sample. Syn-
ingly, the Au 4f7/2 position 共BE⫽84.2 eV, Fig. 5兲 was ⫹0.2 thesis conditions: rf-power⫽5 W, Ar total pressure⫽0.38 mbar, deposition
eV higher than the reference value for bulk metal gold, thus time⫽10⬘.

140 Surface Science Spectra, Vol. 10, 2003 Introduction to XPS Studies

FIG. 6. XPS depth profiles of two Au/TiO2 specimens obtained under the
following conditions: rf power⫽25 W, Ar total pressure⫽0.38 mbar, depo-
sition time⫽10⬘. 共a兲 As-prepared; 共b兲 annealed ex situ at 600 °C for 60⬘ in
air (Ar⫹ sputtering at 2.5 kV, Ar partial pressure ⫽5⫻10⫺8 mbar; rastered
area ⫽2⫻2 mm2).
nm兲 and thermally induced coalescence of gold agglomer-
ates. XPS analyses showed the absence of Au/TiO2 chemi-
cal interactions and provided evidence for the dispersion of
metal gold particles 关BE共Au 4 f 7/2 )⫽84.0 eV兴 in the titania
matrix after thermal treatment 共Ref. 37兲. Surface investiga-
tion revealed a double-component structure for the O 1s
peak. The major contribution 共BE⫽530.2 eV兲 was that of
lattice TiO2 oxygen, while a second band at BE⫽531.3 eV
was related to –OH groups arising from atmospheric expo-
sure. In fact, the latter component was reduced to noise
level after a mild Ar⫹ sputtering 共Ref. 37兲. Irrespective of
the annealing conditions, the Ti 2p 3/2 peak position 共BE
⫽459.0 eV兲 confirmed the formation of Ti共IV兲 oxides. In-
terestingly, XPS depth profiling evidenced Au penetration
in the sub-surface titania layers already in the as-prepared
samples 关Fig. 6共a兲兴, due to the synergy between the xerogels
porosity and the infiltration power typical of plasmochemi-
Surface Science Spectra, Vol. 10, 2003
cal methods. In this case, carbon presence was detected
throughout the investigated thickness, indicating an incom-
plete TiO2 network formation. In a different way, after an-
nealing at 600 °C 关Fig. 6共b兲兴 C contamination was merely
limited to the near-surface layers. Moreover, an apparently
lower average gold amount was observed and attributed to
thermally induced Au particle agglomeration 共Ref. 20兲.
Finally, a study of Ag/SiO2 nanocomposites obtained by
rf sputtering of silver from Ar plasmas on amorphous silica
was undertaken 共Ref. 21兲. Once again, deposition experi-
ments were performed at temperatures as low as 60 °C, in
order to minimize any possible thermal effect with respect
to plasma-dependent phenomena.
The obtained results evidenced the formation of silver-
based nanosystems 共average crystallite size ⭐10 nm兲,
whose features 共metal content, Ag particle size and shape,
structure and optical properties兲 could be carefully tailored
by controlled variations of the synthesis parameters 共Ref.
21兲. Unlike the case of gold-based nanosystems, XPS in-
vestigations showed the presence of chemical species
different from metallic silver 共Ref. 38兲. In fact, the silver
Auger parameter values 关␣1⫽BE共Ag 3d5/2兲⫹KE共Ag M5
VV兲; ␣2⫽BE共Ag 3d5/2兲⫹KE共Ag M4VV兲兴 fell in between
Ag共0兲 and Ag共I兲 reported data ( ␣ 1 ⫽720.0 eV; ␣ 2 ⫽725.4
eV兲 共Refs. 21 and 32兲.
Such phenomena are confirmed by the C 1s and O 1s
spectra of an Ag/SiO2 specimen 共Fig. 7兲. In particular, the
C 1s photopeak 关Fig. 7共a兲兴 was characterized by two com-
ponents: the main one 共BE⫽284.8 eV兲, ascribed to the pres-
ence of adventitious carbon, and another one 共BE⫽287.8
eV兲 attributed to carbonates or bicarbonates arising from
atmospheric exposure 共Ref. 21兲. Similar attributions were
supported by the analysis of the O 1s signal 关Fig. 6共b兲兴,
characterized by a component at BE⫽533.0 eV due to the
silica substrate and a lower BE peak at 531.1 eV mainly
ascribable to Ag2CO3/AgHCO3 . However, other species
could also be responsible for the latter band, including hy-
droxyl groups and adsorbed H2O/O2 共Refs. 21 and 38兲.
As a general rule, lower silver particle sizes corre-
sponded to a more marked formation of carbonate/
bicarbonates on the cluster external shells, indicating an
enhanced reactivity with the atmosphere due to their nano-
structure.
CONCLUDING REMARKS
This introduction was aimed at presenting an overview
on XPS studies of metal and metal-oxide nanosystems re-
cently synthesized by our research group. In particular, at-
tention was focused on nanostructured oxide thin films
(LaCoO3), oxide clusters in silica matrices (HfO2 and
HfO2 – ZrO2 in SiO2) and metal cluster-containing compos-
ites 共Au/HOPG, Au/TiO2 , and Ag/SiO2). As a general rule,
XPS has proved to be an effective tool for the chemical
investigation of these systems. In fact, the performed analy-
ses have yielded interesting information concerning the
chemical nature of the species as well as the surface and
in-depth system composition.
The core-level spectra collected in this issue and the
related tables of spectral features represent a useful collec-
Introduction to XPS Studies 141

FIG. 7. Surface C 1s 共a兲 and O 1s 共b兲 photoelectron peaks for a represen-
tative Ag/SiO2 specimen. Synthesis conditions: rf power⫽25 W, Ar total
pressure⫽0.38 mbar, deposition time⫽10⬘.
tion for researchers working on XPS analyses of nanosys-
tems, both for research and industrial purposes.
ACKNOWLEDGEMENTS
National Research Council 共CNR兲 and Padova Univer-
sity are acknowledged for financial support. We are also
indebted to research programs FISR-MIUR ‘‘Nanotecnolo-
gie molecolari per l’immagazzinamento e la trasmissione
delle informazioni’’, FISR-MIUR ‘‘Nanosistemi inorganici
ed ibridi per lo sviluppo e l’innovazione di celle a combus-
tibile’’ and FIRB-MIUR ‘‘Manipolazione molecolare per
macchine nanometriche’’. Prof. S. Barreca is gratefully ac-
knowledged for her valuable comments on the language
used.
142 Surface Science Spectra, Vol. 10, 2003
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Introduction to XPS Studies