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A sol–gel approach to nanophasic

copper oxide thin films
Davide Barreca

Thin Solid Films

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 Thin Solid Films 442 (2003) 48–52

A sol–gel approach to nanophasic copper oxide thin films

Lidia Armelaoa,*, Davide Barrecaa, Manuel Bertapelleb, Gregorio Bottarob, Cinzia Sadac,
Eugenio Tondellob
a
ISTM-CNR and INSTM, Department of Chemistry, University of Padova, via Marzolo, 1, Padova, Italy
b
Department of Chemistry and INSTM, University of Padova, via Loredan, 4, Padova, Italy
c
INFM and Department of Physics, University of Padova, via Loredan, 9, Padova, Italy

Abstract

Nanostructured copper oxide films were prepared via sol–gel starting from ethanolic solutions of copper (II) acetate
wCu(CH3COO)2ØH2Ox. Films were obtained by dip-coating at room temperature in air and were subsequently heat-treated at
different temperatures (100–900 8C) in oxidizing (air), inert (N2 ) or reducing (4% H2 in N2) atmospheres. The evolution of the
oxide coatings under thermal treatment was studied by glancing incidence X-ray diffraction, X-ray photoelectron spectroscopy
and X-ray excited Auger electron spectroscopy. Different crystalline phases were observed as a function of the annealing
conditions. Depending on both temperature and atmosphere, the film composition resulted single- or multi-phasic. All the layers
were nanostructured with an average crystallite size lower than 20 nm. The most relevant results concerning sample composition
and microstructure as well as their mutual relations with the synthesis conditions are presented and discussed.
䊚 2003 Elsevier B.V. All rights reserved.

Keywords: Copper oxides; Nanosystems; Sol–gel; Thin films

1. Introduction and for the photocatalytic decomposition of water w14x.

Copper oxide-based materials have been widely inves-
tigated due to their potential applications in many
technological fields. Cupric oxide (CuO, tenorite) is a
monoclinic p-type semiconductor with a band gap of
1.2–1.5 eV w1–3x, whereas cuprous oxide (Cu2O,
cuprite) is a cubic p-type semiconductor with a band
gap of 2.0 eV w3,4x.
Copper oxides and metallic copper have been
employed as heterogeneous catalysts for several envi-
ronmental processes, e.g. NO selective reduction, CO
oxidation and NO2 decomposition w5–8x. Furthermore,
copper (II) oxide thin films could be employed in the
production of gas sensing devices, owing to the conduc-
tivity changes induced by the reaction of gases with
surface adsorbed oxygen w9,10x. Conversely, when com-
bined with small noble metal particles, copper (II) oxide
displays high activity as optical gas sensor w11,12x.
Regarding Cu2O, it is a very promising material for the
development of photovoltaic devices like solar cells w13x
*Corresponding author. Tel.: q39-49-827-5236; fax: q39-49-
8275-161.
E-mail address: armelao@chin.unipd.it (L. Armelao).
On this basis, a deeper insight into the chemico–physical
properties of such systems and their dependence on the
synthetic routes can lead to the optimization of func-
tional performances. In this context, the inherent synergy
of large surface area and high defect content displayed
by nanosystems is expected to result in improved prop-
erties with respect to the conventional ones w15x. To this
aim, the sol–gel technique plays an outstanding role as
a soft bottom-up approach to achieve a good control
over film composition and microstructure.
This paper is focused on the sol–gel synthesis and
characterization of nanocrystalline copper oxide thin
films. To the best of our knowledge, only few works
are available in the literature w13,16x.
In the preparation of such systems, stoichiometry and
phase composition represent a major concern. Further
aspects, such as crystallite size and distribution, can be
suitably tailored by a proper choice of the molecular
precursors and of the annealing conditions. Particular
attention was focused on the chemical and microstruc-
tural evolution of the systems as a function of the
annealing treatment, e.g. temperature, time and
atmosphere.

0040-6090/03/$ - see front matter 䊚 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0040-6090(03)00940-4
 L. Armelao et al. / Thin Solid Films 442 (2003) 48–52 49

The microstructural evolution was studied by glancing

incidence X-ray diffraction (GIXRD), while the chemi-
cal composition and copper oxidation state were inves-
tigated by X-ray photoelectron spectroscopy (XPS) and
X-ray excited Auger electron spectroscopy (XE-AES).

2. Experimental

In this work copper (II) acetate was used as a starting

compound. The choice was made taking into account
that the hydrolysis of acetate groups gives products
soluble in the solvent medium and easily decompose
into volatile compounds under annealing.
As far as the preparation of copper oxide thin films
was concerned, the best results were achieved starting
from a precursor solution obtained dissolving copper
acetate (Cu(CH3COO)2ØH2O, Aldrich, 98%) in ethanol
(C2H5OH, Carlo Erba, 99.8%). The prepared solution
(cCuOf10 gyl) was stirred at room temperature for at
least 1 h before film deposition.
The films were obtained by a dip-coating procedure.
Herasil silica slides, supplied by Heraeus, were used as
substrates. Before use, the slides were cleaned according
to a well-established procedure w17x, aimed at favoring
the best adhesion of the layers on the substrates.
Film deposition was carried out in air at room
temperature with a controlled withdrawal speed of
approximately 7 cm miny1. Coatings were obtained by
means of a multi-dipping process, up to seven deposi-
tions, without any thermal treatment between them. The
as-prepared samples resulted homogeneous; well-adher-
ent to the substrates, transparent, crack free and pale
blue coloured.
The obtained films were subsequently heated in a
horizontal tube furnace (Gero) at temperatures between
100 and 900 8C with a temperature accuracy of 1 8C.
The time of treatment was varied between 1 and 5 h in
three different flowing gas atmospheres, i.e. air, nitrogen
(purity 5.0) and forming gas (4% H2 in N2, purity 5.0).
After annealing at 600 8C the film thickness was f100
nm.
The film structural evolution was studied as a function
of the annealing conditions (temperature, time and
atmosphere) by means of glancing incidence X-ray
diffraction.
GIXRD measurements were performed with a D8
ADVANCE Bruker diffractometer equipped with a Cu-
Ka source (40 kV, 40 mA) and a Gobel ¨ mirror, at a
fixed incidence angle of 1.58. The angular accuracy was
0.0018 and the angular resolution was better than 0.018.
The crystallite dimensions were estimated for all the
samples by Scherrer equation.
XPS spectra were run on a Perkin–Elmer F 5600ci
spectrometer using monochromatized Al-Ka radiation
(1486.6 eV). The working pressure was -5=10y8 Pa.
The spectrometer was calibrated assuming the binding
Fig. 1. GIXRD spectra for samples annealed in air under different
conditions. The observed diffraction peaks correspond to the tenorite
CuO crystal phase.
energy (BE) of the Au4f7y2 line at 83.9 eV with respect
to the Fermi level. The standard deviations for the BE
values were "0.15 eV. Charge neutralization with a low
energy electron flood gun was adopted. The residual
shift on the reported BE values were corrected assigning
to the C1s line of adventitious carbon a value of 284.8
eV w18x.
Wide scan spectra (survey) were obtained in the
range 0–1350 eV. Detailed scans were recorded for C1s,
O1s, Cu2p and CuLMM regions. The different copper
oxidation states were evaluated using the Auger a
parameter w19x, defined as the sum of the BE value of
the Cu2p3y2 XPS band and the kinetic energy (KE) of
the CuLMM Auger peak. The atomic compositions were
evaluated using sensitivity factors provided by F V5.4A
software supplied by Perkin–Elmer w19x. Depth profiles
were carried out by Arq sputtering at 3.0 keV with an
argon partial pressure of 5=10y6 Pa. The samples were
introduced directly, by a fast entry lock system, into the
XPS analytical chamber.
3. Results and discussion
Copper oxide thin films were preliminarily investi-
gated by GIXRD. Fig. 1 displays the XRD spectra of
the films heated in air. At temperatures higher than 400
8C, two reflections at 2uf35.58 (N002M, Ny111M) and
2uf 38.78 (N111M) were observed in the diffraction
patterns and were ascribed to the formation of the CuO
monoclinic crystal phase (tenorite) w20x. Moreover, an
50 L. Armelao et al. / Thin Solid Films 442 (2003) 48–52

annealed in air in analogous conditions evidenced no

differences in the crystallite dimensions.
Further information on the formation and stability of
CuO and Cu2O was gained from the analysis of the
samples annealed in forming gas atmosphere. The results
are displayed in Fig. 3.
The microstructural evolution of the system under
mild reducing conditions is slightly different from the
one observed in nitrogen. For the samples annealed in
air or nitrogen, the crystalline phase was tenorite (CuO)
in a wide range of temperature and time. Conversely,
on annealing in forming gas, a weak reflection associ-
ated to the Cu2O crystalline phase was detected in the
diffraction pattern of the sample heated at 500 8C.
Higher temperatures (900 8C) and prolonged heating
times (3 h) led to a decrease in the intensity of Cu2O
reflections and to an increase in tenorite lines. Finally,
the diffraction pattern of the sample treated for 5 h
showed the co-existence of three crystalline phases, i.e.
CuO, Cu2O and metallic copper w22x.
This behavior suggests a more complex microstruc-
tural evolution under annealing in forming gas flow. As
Fig. 2. Diffraction spectra for samples annealed in N2. The markers a matter of fact, both CuO and metallic copper might
in figure indicate the CuO (h) and Cu2O (*) crystal phases. be formed from cuprite, probably due to redox processes
occurring as a consequence of the Cu2O nanocluster
reactivity under reducing atmosphere.
increase either in the annealing time or temperature To clarify the observed phenomena, the sample
induced a stepwise increase in the diffraction peak annealed at 900 8C for 5 h in nitrogen (showing only
intensities. Irrespective of the treatment temperature, all the Cu2O phase) was treated under the same conditions
samples resulted nanostructured with an average crys-
tallite size of approximately 20 nm. This phenomenon
suggested that no crystallite growth occurred under more
severe annealing conditions. The intensity increase in
the tenorite reflections was attributed to a progressive
crystallization of cupric oxide.
The CuO crystal phase was the only Cu–O form
observed in air. To study the formation of different
crystalline phases containing reduced copper species,
the as-prepared samples were heated both in N2 and
forming gas (4% H2 in N2) flow.
Fig. 2 displays the evolution of the GIXRD spectra
for samples annealed at temperatures between 500 and
900 8C in nitrogen. In accordance with the results
obtained in air, the tenorite phase was the most stable
up to 900 8C and 1 h treatment. Prolonged treatments
at 900 8C produced a progressive conversion of CuO to
Cu2O. As a matter of fact, in the GIXRD pattern of the
sample heated for 3 h, besides the reflections due to the
tenorite phase, also two weak diffraction lines at 2uf
36.48 (N111M) and 2uf42.38 (N200M) were observed
and attributed to the Cu2O (cuprite) crystalline phase
w21x. Such a conversion resulted complete after 5 h
annealing and cuprite crystallites with a mean diameter Fig. 3. GIXRD spectra for samples annealed in forming gas under
size of approximately 20 nm were observed. A compar- different conditions. The markers in figure indicate the CuO (h),
ison with the diffraction data collected for the sample Cu2O (*) and Cu (⽧) crystal phases.
 L. Armelao et al. / Thin Solid Films 442 (2003) 48–52 51

In the spectra reported in Fig. 5, the Cu2p3y2 peak

Fig. 4. GIXRD patterns for a film heated firstly at 900 8C for 5 h in
N2 and then at 900 8C for 5 h in forming gas.
position for the sample containing only the Cu2O crys-
talline phase (see Fig. 2) showed an intermediate value
between those reported for Cu (I) and Cu (II) oxides
w25x. This finding may indicate the formation of CuO
in the outer layers of the film due to partial oxidation
of Cu(I). In fact, the Cu:O atomic ratio was always
close to 1 on the sample surface.
Further indication of Cu2O and CuO co-presence
might be traced back to the intensity ratio between each
spin-orbit split component and the corresponding shake-
up satellite. The analysis of the Cu2p bandshape profile
for the two specimens indicated a lower intensity ratio
for the sample annealed in N2 (Fig. 5), suggesting thus
the co-existence of Cu(I) and Cu(II) species on the
sample surface. Moreover, the Auger a parameters for
the films annealed in air and nitrogen resulted in 1851.6
eV and 1849.7 eV, respectively (see Fig. 5). A compar-
ison with literature values for CuO (1851.8 eV) and
Cu2O (1848.7–1849.4 eV) w18,25x confirmed unambig-
uously the presence of both copper oxides in the near-
surface region of the film annealed under inert
atmosphere.
The absence of CuO reflections in the corresponding
XRD pattern (see Fig. 2) could be ascribed either to a
little CuO amount, to small cluster sizes or to a low
cristallinity degree.

(900 8C, 5 h) in forming gas. The diffraction pattern of 4. Conclusions

this sample (Fig. 4) evidenced the total disappearance Copper oxide films were prepared by sol–gel dip-
of the Cu2O crystal phase, along with the rise of intense coating on silica slides. The thermal annealing of the
CuO reflections and weak Cu signals.
In order to investigate the mutual relations between
microstructure and chemical composition, the above
specimens were characterized by XPS and XE-AES. It
is worth highlighting that, differently from XRD analy-
sis, both crystalline and amorphous phases are detected
by photoelectron spectroscopies.
In the XPS spectra all samples revealed signals from
Cu, O and C. The latter was ascribed to atmospheric
contamination (ca. 20 at.% on the surface), as indicated
by its disappearance after mild Arq sputtering. Detailed
Cu2p region scans for the samples containing only CuO
(600 8C, 1 h, air) or Cu2O (900 8C, 5 h, N2) crystalline
phases are displayed in Fig. 5.
The discrimination between Cu(II) and Cu(I) oxides
is usually accomplished by the analysis of the Cu2p
region, not only for the different peak position
(Cu2p3y2(CuO)s933.7 eV, Cu2p3y2(Cu2O)s932.5 eV)
w18,23x but also for the bandshape profile. The Cu2p
signals for Cu(II)-containing compounds are character-
ized by the presence of intense shake-up satellites
located at BE values 9 eV higher than the main spin-
orbit split components w24,25x. Conversely, in the case
of cuprous derivatives shake-up satellites are almost Fig. 5. XPS Cu 2p region for samples treated under air or nitrogen in
undetectable. different conditions.
52 L. Armelao et al. / Thin Solid Films 442 (2003) 48–52
as-deposited layers, performed in the 100–900 8C inter-
val under different atmospheres, i.e. air, N2 and forming
gas (4% H2 in N2) led to the formation of different
crystalline phases. Annealing in air resulted in the
formation of tenorite (CuO) even under prolonged
treatments (5 h) at temperatures (900 8C) close to the
decomposition point of bulk CuO (1030 8C) w26,27x.
The formation of CuO crystallites was observed also
in the samples annealed under inert atmosphere (N2) up
to 3 h. A prolonged treatment (5 h) in the same
environment resulted in the complete disappearance of
tenorite and in the formation of a pure cuprite (Cu2O)
crystalline phase.
Finally, under reducing conditions, the formation of
CuO, Cu2O and Cu was progressively observed, leading
to a mixture of Cu(II) and Cu(I) oxides and metallic
copper after treatment at 900 8C for 5 h. In this regard,
recent studies w28x have demonstrated that the co-
presence of copper oxides results in a synergic effect in
oxidation catalytic processes of ethanol.
Irrespective of the thermal annealing, all the obtained
films resulted nanostructured with an average crystallite
size lower than 20 nm. These results indicated that,
under the adopted conditions, nucleation was predomi-
nant over the subsequent crystallite growth, thus allow-
ing tailoring of composition and crystallite dimensions
by a proper choice of processing conditions. The for-
mation of nanosized single-phase copper oxide coatings
and the Cu2O behavior under reducing conditions are
currently under investigation.
Acknowledgments
This work was partially funded by Progetto Finaliz-
zato ‘Materiali Speciali per Tecnologie Avanzate II’ of
the CNR (Rome) and Consorzio OPTEL-PNR Art. 10
legge 46y1982.
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