Chemical Vapor Deposition of Cu
2
O and CuO
nanosystems for innovative gas sensors
Elisabetta Comini, Giorgio Sberveglieri,
INFM-CNR, SENSOR Lab,
Department of Chemistry and Physics, Brescia University,
Brescia, Italy
comini@sensor.ing.unibs.it
Davide Barreca,
ISTM-CNR and INSTM,
Department of Chemistry, Padova University, Padova,
Italy;
Cinzia Sada,
INFM and Physics Department, Padova University,
Padova, Italy.
Alberto Gasparotto, Chiara Maccato,Eugenio Tondello
Department of Chemistry,
Padova University and INSTM,
Padova, Italy;
Abstract— Supported copper oxide nanosystems (Cu
x
O, x=1,2)
were synthesized by Chemical Vapor Deposition (CVD) on
Al
2
O
3
substrates. Structural and morphological characterization
showed an evolution from polycrystalline Cu
2
O granular films
to CuO samples with an entangled quasi 1-D morphology upon
increasing the growth temperature from 350 to 550°C. For the
first time, CVD copper oxide nanosystems were investigated in
the gas sensing of CH
3
COCH
3
and CH
3
CH
2
OH. The analyses
revealed appreciable responses even at moderate operating
temperatures, with characteristics directly dependent on the
system composition and nano-organization.
I. INTRODUCTION
The p-type multi-functional copper oxides (Cu
2
O and
CuO) have been investigated for various applications, from
solar energy conversion to photovoltaics, from catalysis to
solid state gas sensing. Especially in the latter field, organized
nanostructured materials, such as nanorods and nanoribbons,
feature unique functional properties [1-3], that are
significantly advantageous in order to achieve high analyte
sensitivity and a rapid response [4]. Nevertheless, the majority
of reports has been focused on the use of n-type
semiconductors, while the gas sensing properties of supported
nano-organized p-type Cu
x
O (x=1,2) deserve further studies
[3,5]. The aim of the present contribution is to highlight the
performances of copper oxide nanosystems obtained by CVD
in solid state gas sensors as a function of their chemical
composition and nano-organization.
II. EXPERIMENTAL
A. Deposition details
Copper oxide nanodeposits were synthesized by means of
a custom-built cold-wall CVD reactor under electronic grade
O
2
-based reaction atmospheres, using Cu(hfa)
2
•TMEDA (hfa
= 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA =
N,N,N’,N’-tetramethylethylenediamine) as Cu precursor for
the first time. Basing on previous results [6], the deposition
conditions adopted in the present work are summarized in
Table I.
TABLE I. LIST OF TESTED SAMPLES.
Sample
code
Deposition conditions
Cu2O Growth T=350°C O2+H2O
CuO Growth T=550°C O2
10 mbar
Alumina substrates (3×3 mm
2
) were used for the
preparation of gas sensors. Depositions were performed using
a precursor heating temperature of 70°C, with a total O
2
flow
rate of 200 sccm (total duration=2 h). For the growth
experiments carried out in the presence of H
2
O vapor, a water
bath kept at 50°C was connected to the gas-line. The gas lines
between the precursor vaporizer and the reaction chamber
were maintained at 120°C throughout each deposition in order
to prevent undesired precursor condensation phenomena. At
the end of each experiment, samples were cooled down to
room temperature under flowing O
2
.
B. Characterizations
Glancing Incidence X-ray Diffraction (XRD)
measurements were performed at a constant incidence angle of
0.5° by means of a Bruker D8 Advance diffractometer,
equipped with a Göbel mirror and a Cu Kα source powered at
40 kV, 40 mA. The angular accuracy was 0.001° and the
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