Physica B 406 (2011) 144–149

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Physica B
journal homepage: www.elsevier.com/locate/physb

CO gas sensing of CuO nanostructures, synthesized by an assisted

solvothermal wet chemical route
Alireza Aslani n, Vahid Oroojpour
Department of Chemistry, Faculty of Science, Vali-E-Asr University, Rafsanjan, P.O. Box 77176, Islamic Republic of Iran

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

Article history: CuO nanostructures with different morphologies and sizes were grown in a controlled manner using a
Received 28 June 2010 simple low-temperature hydrothermal technique. By controlling the pH of reaction mixture, spherical
Received in revised form nanoparticles and cloudlike CuO structures were synthesized at 100–150 1C with excellent efficiency.
24 September 2010
These CuO nanostructures have been tested for CO gas monitoring by depositing them as thick films on an
Accepted 27 September 2010
interdigitated alumina substrate and evaluated the surface resistance of the deposited layer as a function
of operating temperature and CO concentrations. The gas sensitivity tests have demonstrated that the
Keywords: CuO nanostructures, especially cloudlike morphology, exhibit high sensitivity to CO proving their
CuO applicability in gas sensors. The role of the nanostructure on the sensing properties of CuO is also
Metal oxides
discussed.
CO gas sensor
& 2010 Elsevier B.V. All rights reserved.
Solvothermal

1. Introduction
Nanostructure metal oxides have been attended in the field of
nanotechnology both from a fundamental and industrial point of
view. For example, their peculiar electrical properties make them
suitable as active sensing materials in resistive sensors, with
enhanced performance with respect to bulk materials [1]. The
ability to control the particle size of metal oxide nanoparticles is of
crucial importance in this respect [2–6]. Great attention is also
addressed to the particle morphology and shape [2]. Various shapes
can exhibit completely different physical properties and perfor-
mances; therefore it is often highly desirable to have pure materials
with controlled morphology. However, controlling the morphology
of materials is not simple as controlling their particle size, yet. As a
matter of fact, there is considerable interest in developing novel
methods for the preparation of metal oxide nanoparticles posses-
sing particular morphological properties and shape for potential
applications in gas sensing [7–9]. Moreover, for practical applica-
tions, the main challenge consists in finding cost-effective and
scalable synthesis methods for the production of these nanostruc-
tures. On the basis of these considerations, syntheses of metal oxide
nanostructures by chemical processes are more suited compared to
physical ones. Due to the well-known surface conductivity of CuO, a
great deal of attention has been given to this material for gas sensor
applications. In order to enhance the sensing properties of copper-
oxide-based resistive gas sensors, suitable CuO nanostructures
n
Corresponding author. Tel.: + 98 391 3202441; fax: + 98 391 3202429.
E-mail address: a.aslani@vru.ac.ir (A. Aslani).
with controlled size are preferred [10–15]. Both theoretical and
experimental works have been carried out in order to elucidate the
relation between the sensitivity and the microstructure of CuO for
gas sensors. Moreover, many researchers found that the sensor
based on sol–gel processed nanopowders is more sensitive to CO
than that based on nanotetrapods. To rationalize the behavior of
metal oxide nanostructures, Yamazoe and Shimanoe [16] and Hyun
Seo et al. [17] developed a new general model on the roles of shape
and size of crystals in semiconductor resistive gas sensors on the
basis of electron-depleted conditions. The model proposed con-
firms that the gas sensitivity increases with decrease in the crystal
size as it was experimentally proven for many cases, and predicts
that crystals in spherical shape would show higher sensitivity than
those in columnar shape. However, the effect of the nanostructure
on the sensing properties in metal-oxide-based resistive gas
sensors is not yet fully understood and requires further investiga-
tions. Recently, Krishnakumar et al. [18–20] reported the prepara-
tion of different copper oxide nanostructures (spherical and
cloudlike) by a microwave-assisted synthesis.
On the other hand, in recent years, copper oxide (CuO) has
received extensive investigations for its prospective applications in
many fields. CuO is a p-type semiconductor with a narrowband gap
of 1.4 eV [21]. It has similar properties with high-Tc super-
conducting copperates but consists of Cu–O bonding only; hence
it has been used as a basic material in high-Tc superconductors
[22,23]. It can also be used potentially in gas sensors, solar cells, FE
emitters, electronic cathode materials and catalysts in organic
reactions [24–28]. Many methods have been developed to prepare
CuO with various morphologies. Liu and Bando [29] synthesized
nanodendrite like CuO via hydrothermal route. CuO nanoshuttle

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.09.038
 A. Aslani, V. Oroojpour / Physica B 406 (2011) 144–149
was also prepared under surfactant assisted conditions using the
same method [30]. CuO nanorods and nanoribbons were synthesized
by wet chemical methods. In addition, the nanofibers of CuO were
prepared by thermal oxidation on Cu substrate by importing the
polycarbonate membrane template for initial deposition of Cu nuclei
[31]. The above mentioned methods cannot be departed from the
complex chemical reactions or processes. Thermal oxidation may
assist the production of catalysts, semiconductor devices or functional
oxide films under controlled conditions [32]. A direct and simple
thermal oxidation method was employed to synthesize CuO nano-
wires and nanorods. Using this convenient route, with no catalyst and
template assisted, many research teams prepared CuO nanowires
successfully by oxidizing copper foils under different conditions such
as different annealing temperatures, time or atmosphere [33–40].
X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX,
TGA-DTA and PL spectra were used to characterize the morphology,
structure and phase of the synthesized nanostructures. In the present
work we report data about CuO nanoparticles gas-sensing properties,
using the active layers in CO gas resistive sensors. The gas-sensing
properties of different nanoparticles were compared and discussed as
a function of morphology of the primary nanoparticles. The results
presented here highlighted the role of the shape of the primary CuO
crystallites, and an explanation based on the characterization and
sensing data obtained has been given.
2. Experimental
The reaction of Cu acetate at different conditions of pH to form
CuO nanostructures is shown in Scheme 1. In a typical procedure,
2 mmol of Cu(Oak)2  2 H2O was added into 20 ml of Eton/CH2Cl2.
The mixture was stirred vigorously for 30 min and desired pH is
reached (Table 1) under vigorous agitation, then mixture was sealed
in a Teflon-lined stainless-steel autoclave. The tank was heated and
maintained at 120–190 1C for 12, 24, 36 and 48 h, and then allowed
to cool down to  10 1C temperature rapidly. The product was
collected by centrifugation and washed with acetone and ethanol
several times to remove the excessive reactants and by products
(Table 1). Then it was calculated under vacuum at 400 1C for 2 h. The
resulting powder was collected for further characterization. X-ray
Scheme 1. Schematic formation of CuO nanostructures by solvothermal method
without any additives.
Table 1
Synthesis parameters and morphology and size of different CuO nanostructures.
Sample Time Temperature pHi pHf Morphology
(h) (1C)
CuO-1 12 120 8 11 Nanoparticle
CuO-2 12 150 9 11 Nanoparticle
CuO-3 24 120 8 11 Cloudlike
CuO-4 24 150 9 11 Cloudlike
145
powder diffraction (XRD) measurements were performed using a
Philips diffract meter of Expert Company with monochromatized
CuKa radiation. The particle sizes of selected samples were esti-
mated using the Sherrer method. The samples were characterized
by a scanning electron microscope (SEM) (Philips XL 30) with gold
coating. The luminescent properties were investigated using an
F-4500 FL spectrophotometer.
2.1. Sensing tests
Sensors were made by depositing the drop coating films
(1–10 mm thick) of the nanopowders dispersed in water on alumina
substrates (8 mm  4 mm) with Pt interdigitated electrodes and a
Pt heater located on the backside. The structure of the fabricated
sensor device is reported elsewhere [41]. Before sensing tests, a
thermal treatment at 400 1C for 2 h was carried out in order to
stabilize the microstructure of the sensing film. The sensors were
then introduced in a stainless-steel test chamber for the sensing
tests. The experimental bench for the electrical characterization of
the sensors allows to carry out the measurements in a controlled
atmosphere. Gases coming from certified bottles can be further
diluted in air at a given concentration by mass flow controllers.
Sensing measurements were carried out in the temperature range
150–400 1C, with steps of 50 1C, under a dry air total stream of
200 sccm, collecting the sensors resistance data in the four point
mode. A multimeter data acquisition unit Agilent 34970A was used
for this purpose, while a dual-channel power supplier instrument
Agilent E3632A was employed to bias the built-in heater of the
sensor to perform measurements at super-ambient temperatures.
The gas response is defined as the ratio Rair/Rgas, where Rair is the
electrical resistance of the sensor in dry air and Rgas the resistance at
different CO concentrations.
3. Result and discussion
In Fig. 1 the SEM micrographs of six typical samples with
distinct morphologies are presented. While Fig. 1a shows the
formation of CuO nanoparticles of about 90 nm average size,
formation of cloudlike particles of about 40–100 nm average
diameter and particles with small cloudlike morphology can be
observed in Fig. 1b. While all these structures were synthesized
almost at the same reaction temperature and time with EtOH/
CH2Cl2 contents, the reactant content in the reaction mixture was
different. It is important to mention that the structures were well
reproducible when the growth parameters were kept unchanged.
However, the size of the nanostructures could be varied to some
extent by varying the reaction time. Though the real mechanism of
formation of such morphologies is debatable, we believe that, by
changing the initial and final pH of the reaction mixture, we varied
the rate of nucleation and growth events. When the difference
between the initial and final pH values is high, the nucleation rate is
high; the formation of nanoparticles occurs at a faster rate and the
supply of the precursors impinging on the particle surface ceases
quickly. While the difference between the initial and final pH
values is low, the nucleation rate is slow and the particles reach
their critical size under the steady flow of precursors. When the
area of c-face in the particle becomes larger than the critical size for
nucleation, further nucleation occurs on it, and the process repeats
to form nanoparticle structures. For the intermediate difference in
Size
(nm) pH values, the nucleation rate is moderate and an anisotropic
columnar growth may proceed by repeated nucleation and epitax-
100 ial growth at the top and side faces of the initial wurtzite structure.
90 In Fig. 2 the XRD spectra of the nanostructures synthesized at
40
40
different initial and final pHs are presented. We can observe the
formation of well crystalline hexagonal CuO for all the samples,
146 A. Aslani, V. Oroojpour / Physica B 406 (2011) 144–149
Fig. 1. Typical SEM micrographs of the samples (a) CuO-1 and CuO-2, (b) CuO-3 and CuO-4, with distinct morphologies.
while the crystallinity of the samples increased on reducing the
difference between the initial and final pH of the reaction mixture.
All the XRD peaks were indexed Fig. 2 and they agreed well with the
standard CuO of hexagonal structure. The XRD patterns of typical
samples of NP-CuO prepared by the solvothermal process are
shown in Fig. 2. The obtained patterns matched with standard
patterns of CuO. The results of XRD powder patterns indicated that
the experimental data are in good agreement with the simulated
XRD powder patterns based on the reference data. Hence these
compounds were obtained as a mono-phase. The broadening of the
peaks indicated that the particles were of nanometer scale.
Estimated from the Sherrer formula, D ¼0.891l/b cos y, where D
is the average grain size, l the X-ray wavelength (0.15405 nm) and
y and b are the diffraction angle and full-width at half maximum of
an observed peak, respectively. Our EDS results revealed excellent
stoichiometry for all the samples.
In Fig. 3 the representative PL spectra of the samples are
presented. In general, the room temperature PL spectra of all the
as-grown and annealed samples revealed similar features. There
appeared two sharp emission bands at about 300 and 680 nm,
generally assigned as a near-band-edge (NBE) emission band and
another broad deep-level emission band extending from 605 to
625 nm. The position of the NBE emission band in our nanostruc-
tures agrees well with the reported value for the nanoparticles
grown by thermal evaporation. Generally, the deep-level emission
in CuO consists of a green emission at around 605 nm and a near-
yellow emission at around 680 nm. Though the origin of the green
emission is controversial, generally it is assigned to the singly
ionized oxygen vacancies. The yellow emission has been related to
the interstitial in CuO. Therefore, the evolution of green and yellow
bands in CuO is competitive with each other. The broad emission
band revealed in the visible region in our samples is due to the
superposition of green and yellow emissions. On air annealing, the
intensity ratio of deep-level emission and NBE emission (Ideep-level/
INBE) decreased from 15.9 to about 0.89 due to annealing of point
defect and defect complexes. The evolution of these bands on
thermal annealing in oxygen atmosphere is under study. On the
other hand NP-CuO showed two strong and sharp bonds at 300 and
680 nm. This result may be explained by the fact that NP-CuO has a
better crystallinity in its nanosize form and these emission peaks are
virtually the same, indicating that they are influenced by the size of
particles. As compared with the other methods used for preparing
CuO nanoparticles, the solvothermal method is very fast and does
not need any additives and surfactants during the reactions.
To investigate the size distribution of the nanoparticles, a particle
size histogram was prepared for CuO nanoparticles (Fig. 4). Most of
the particles possess sizes in the range of 40–100 nm. For further
demonstration, EDAX was performed for the samples. The EDAX
spectra of NP-CuO in Fig. 5 show the presence of Cu and O as the only
elementary components.
The electrical characteristics of the CuO nanostructures depos-
ited as thick films on alumina substrates have been also investi-
gated. As an example, Fig. 6 report the variation in resistance in the
temperature range 25–350 1C for the sample CUA after a heating–
cooling cycle in dry air. All prepared films exhibited similar
behavior, characterized by a negative temperature coefficient of
electrical resistance, which is consistent with a semiconducting-
type behavior. At room temperature the resistance of the as-
prepared CUA film was very high and was not measurable with a
conventional resistance meter. After heating (red line), the resis-
tance decreased due to the thermal activation of electron charge
carriers. The initial high electrical resistance of the as-prepared
sample can be attributed to the water adsorbed during storage at
room conditions, which causes the formation of hydroxyls on the
CuO surface. They attract electrons from the bulk and become
negatively charged and give rise to a positive space charge region
leading to a high electrical resistance [42]. On the other hand in the
successive cooling cycle (blue line), the sample displayed lower
electrical resistance in all temperature ranges. This was likely
associated with the de-hydroxylation of the surface occurred
during the heating cycle. Repeating heating–cooling cycles in dry
air, a fully reversible behavior with negligible hysteresis was
observed, due to the structural stability of CuO surface layer in
dry air in the investigated temperature range.
 A. Aslani, V. Oroojpour / Physica B 406 (2011) 144–149 147

Fig. 4. Particle size histogram of CuO nanostructures.

Fig. 5. EDAX analysis of CuO nanoparticles.

Fig. 2. XRD patterns of the CuO nanostructures grown with different pHs (see
samples details in Table 1).

Fig. 6. Heating–cooling curves showing the electrical resistance of CUA film as a

function of temperature.

3.1. CO sensing tests

It is well known that the response of resistive sensors is highly

affected by the operating temperature. Therefore, the response of
the CuO sensors as a function of operating temperature was first
investigated. Fig. 7 shows the response as a function of operating
Fig. 3. PL spectra of sample a. temperature from 150 to 400 1C for the CUH sensor exposed to
148 A. Aslani, V. Oroojpour / Physica B 406 (2011) 144–149
Fig. 7. Response to 400 ppm of CO vs. the operating temperature of the CUH sensor.
Fig. 8. Transient response of CUH sensor to exposure of 100 ppm of CO at 300 1C.
400 ppm of CO. A rapid increase in the response was observed as
the working temperature was increased and reached a maximum at
about 300 1C and started decreasing thereafter. This characteristic
volcano curves can be interpreted on the basis of adsorption–
desorption and reaction processes occurring on the sensing layer
surface. For operating temperatures o200 1C the sensor response
is low because the adsorbed CO molecules are not activated enough
to react with the surface adsorbed oxygen species. An increase in
operating temperature above 200 1C contributes to overcome the
activation energy barrier of the reaction and a significant increase
in electron concentration results from the sensing reaction
(COads + [O]-CO2 +e  ). However, above 300 1C the decrease in
CO gas adsorption is not adequately compensated by the increase
in surface reaction and the sensor response decreases. The transient
response was found reversible (Fig. 8). The response time, tres,
defined here as the time required to achieve 90% of the total
resistance change when CO is introduced in air, is fast (tres  25 s). A
slower recovery time, trec, i.e. the time required to achieve 90% of
the total resistance change when CO is turned off and pure dry air is
re-introduced into the chamber, has been observed (tres  150 s).
The response as a function of CO gas concentration for all the CuO
sensors investigated at 300 1C is shown in Fig. 9. The sensors show a
good response to CO. The response increased as the CO gas
Fig. 9. Response to different CO gas concentrations for CuO sensors at 300 1C.
concentration was increased from 100 to 500 ppm. Fig. 10a shows
the sensor responses vs. CO concentration. A linear trend was
observed, when responses are plotted in a log–log scale, as a
function of gas concentration. It is interesting to observe that all the
nanostructure films display the same sensitivity to CO, SCO, as
calculated by the slope of the extrapolated straight lines reporting
the response as a function of CO concentration in Fig. 10b. The
sensitivity with respect to CO was calculated to be 0.012 ppm  1.
Instead, the responses at a given CO concentration and the
detection limits, DL, defined as the lower concentration in which
the response significantly differentiated from the noise signal, i.e. 3
times the standard deviation of noise (instrumental detection
limit), are different among the investigated sensors. CUH sensor,
based on cloudlike particles, exhibits a slightly greater response
than other sensors with various morphology particles, while on
CUA sensor (nanoparticle) the lower response was found, and the
same trend was found for the detection limits. The extrapolated
limit of detection for the CUH sensor is about 0.5 ppm, allowing the
monitoring of CO down to concentrations in the sub-ppm range.
Even though a direct comparison with recent literature reports on
CO sensing of various CuO nanostructures cannot be made because
of the different experimental conditions adopted, the results we
obtained clearly indicate the good performances of our sensors.
4. Conclusions
A simple wet chemical process assisted by solvothermal method
was proposed for the synthesis of different CuO nanostructures for
gas-sensing applications. Moreover, by changing the synthesis
parameters CuO nanostructures with different shape/morphology
can be obtained. These nanostructures were investigated in the
monitoring of carbon monoxide, showing the maximum of
response at around 300 1C. The higher response was obtained for
the CUH sensor based on CuO nanoparticles exhibiting cloudlike
morphology. A synergic effect between small crystallite size/high
surface area and potential barrier modification is proposed to
explain the enhanced sensing properties of the CuO particles with
cloudlike morphology. In summary, from this study, it can be
deduced that the performance of resistive CuO based sensors to CO
gas can be controlled by tuning the morphology of the metal oxide
nanoparticles by a rapid synthesis procedure assisted by the
solvothermal method, providing a simple way to fabricate highly
sensitive CO gas sensors.
 A. Aslani, V. Oroojpour / Physica B 406 (2011) 144–149 149

Fig. 10. (a) Calibration curves of CuO sensors at 300 1C; (b) calibration curves of CuO sensors showing the measured sensitivity to CO and the extrapolated detection limit
related to CUH sensor.

Acknowledgements [19] T. Krishnakumar, R. Jayaprakash, V.N. Singh, A.R. Phani, J. Phys. Chem. Solids,
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