Journal of Alloys and Compounds 654 (2016) 202e208

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Enhanced ammonia sensing characteristics of Cr doped CuO

nanoboats
S. Bhuvaneshwari, N. Gopalakrishnan*
Thin Film Lab, Department of Physics, National Institute of Technology, Tiruchirappalli, 620 015, India

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

Article history: Here, we report a room temperature NH3 sensing prototype with an enhanced sensitivity utilizing
Received 22 May 2015 undoped CuO nanorods (NRs) and Cr doped (2 at.% and 6 at.%) CuO nanoboats (NBs) synthesized by a
Received in revised form simple hydrothermal method. Deep level emissions were observed in the range of 350e610 nm by
31 August 2015
photoluminescence analysis. The observed green emission in Cr doped samples indicates the presence of
Accepted 6 September 2015
oxygen vacancies which are induced by doping. Electrical measurements confirmed the ohmic contact of
Available online 9 September 2015
the samples with Ag electrode. The temperature and gas concentration dependence on the sensing
properties demonstrated that the addition of Cr significantly enhanced the sensing performance towards
Keywords:
Copper oxide
NH3 in the 100e600 ppm concentration range at room temperature. In the case of 6 at.% Cr doped CuO
Hydrothermal NBs, a 2.5 fold increase in sensor response was observed at room temperature and a maximum sensi-
Nanorods: nanoboats tivity of 180% at 75
C for 600 ppm of NH3. The enhanced sensing response is attributed to the increase in
Gas sensing surface area, surface charge and oxygen vacancies in CuO nanostructures by Cr doping.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Metal oxide semiconductors are one of the most significant
classes of semiconductors owing to their wide & tunable band gap,
low cost, ease of fabrication and non-hazardous nature. In the case
of metal oxide nanostructures, characteristic features such as
higher surface to volume ratio and quantum size effects can be
widely exploited in the fabrication of a variety of electronic, opto-
electronic devices including solar cells, photodiodes and gas sen-
sors [1]. The devices constructed utilizing metal oxide
nanostructures always demonstrated higher figure of merit
compared to its bulk counterparts. Among the several applications,
gas sensing based on solid state devices is on high demand to meet
the technological and industrial demands. In such a device, a
chemical stimulus; for example, the gas concentration is trans-
duced into a readable electrical signal. Chemi-resistive sensors,
with low power consumption and ease of high precision resistance
measurements can be extensively employed in gas sensing
providing major breakthroughs in various fields such as environ-
mental monitoring, agriculture and industry [2].
In comparision with uniform spherical nanoparticles, oriented
metal oxides nanostructures such as nanowires (NWs), nanorods
* Corresponding author.
E-mail address: ngk@nitt.edu (N. Gopalakrishnan).
(NRs) and nanosheets (NSs) are more advantageous for gas sensing
applications. This is attributed to the fact that these nanostructures
possess larger surface to volume ratio and higher aspect ratio which
mainly governs the sensing efficiency [3]. The performance of these
2D nanostructures in gas sensing can be further improved by sur-
face modification and doping using other suitable nanomaterials,
thus providing hetero-interfaces.
Among the various metal oxide semiconductors, CuO is a
promising candidate for efficient room temperature gas sensing.
CuO is an intrinsic p-type semiconductor due to its native Cu va-
cancies. There have been few reports showing the influence of
morphologies on gas sensing properties of CuO nanoparticles to-
wards different oxidizing/reducing gases such as CO, NO2, H2S and
volatile organic compounds such as ethanol, butane, propanol etc.
Liao et al. [4] prepared CuO nanowires based FET devices for the
detection of CO. CuO hollow nanospheres based H2S gas sensor was
fabricated and its sensing performance was demonstrated by Yao-
Qin et al. [5]. Mono-dispersed CuO nanospheres were utilized as
H2S sensors by Zang et al. [6]. CuO nanoplates and nanowires were
found suitable for NO2 detection [7] and air quality control in
automotive cables [8] respectively. In all the studies mentioned
above, the optimum temperatures suitable for sensing operation
are well above the room temperature (30
C). However, room
temperature (RT) operation is more preferred while considering
several advantages for practical applications such as reduced en-
ergy consumption by the sensor, simplified device structure (i.e., no

http://dx.doi.org/10.1016/j.jallcom.2015.09.046
0925-8388/© 2015 Elsevier B.V. All rights reserved.
 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208
heating element is needed) and the convenience of deploying such
sensors in explosive environments where high temperature is un-
desirable. Meanwhile, very few reports are available on the gas
sensing properties of CuO sensor operable at room temperature. For
instance, Dee et al. synthesized CuO nanowires by thermal oxida-
tion method and demonstrated the RT sensing properties of 1%
butane and ethanol vapor independently [9]. Xianghong et al.
fabricated a gas sensor for room temperature detection of ethanol
and methanol using worm-like CuO structures as the active
component [10].
In this paper, we present our results on the modulation of
morphological and electrical properties of CuO nanostructures
synthesized by hydrothermal method on Cr addition. The utiliza-
tion of the prepared CuO nanorods (NRs) and Cr doped CuO
nanoboats (NBs) for room temperature sensing of NH3 gas is mainly
focused.
2. Experimental
2.1. Synthesis of nanostructures
Undoped and Cr doped CuO nanostructures were prepared by a
low temperature hydrothermal route. For the synthesis of undoped
CuO, copper nitrate (CuN2O6. 2.5H2O, 99% purity) was dissolved in
doubly deionized water and kept under vigorous stirring for
20 min. An aqueous solution of sodium hydroxide (NaOH) was
added drop wise and the obtained solution was again stirred for
1.5 h at 80
C. For Cr doped CuO, appropriate amount of copper
nitrate (CuN2O6. 2.5H2O, 99% purity) and chromium chloride (CrCl3.
6H2O, of 99% purity) were dissolved in doubly deionized water to
get 2 and 6 at.% Cr doped CuO nanostructures. Afterwards, the same
procedure as mentioned above was followed. The resultant solution
was transferred to a 200 ml teflon lined autoclave sealed into a steel
tank and kept in furnace at a reaction temperature of 160
C for
12 h. Once the stipulated reaction time over, the autoclave was
naturally allowed for cooling to room temperature. The obtained
precipitate was collected, washed several times with distilled water
and methanol and dried in a laboratory oven at 80
C for 12 h.
The prepared samples were characterized by various tech-
niques. The structural characterization was performed by Rigaku
ultima III X-ray diffractometer (XRD) with Cu Ka radiation of
wavelength 1.5418 Å. Morphological and constituent element an-
alyses were carried out using Field emission scanning electron
microscopy (FE-SEM) with EDS detector and 200 kV transmission
Electron Microscopy (TEM). Band energy and deep level emissions
were observed using a JASCO FP 8500 Spectro fluorometer (room
temperature photoluminescence) with an excitation wavelength of
350 nm. Electrical characterization (IeV) was done using a Keithley
6517A electrometer.
2.2. Gas sensing experiment
The gas sensing ability of the synthesized undoped and Cr doped
CuO nanostructures was examined for NH3 in an indigenously
designed gas sensing setup and the experimental procedures were
maintained similar to that reported by us elsewhere [11]. For
sensing measurements, glass substrates were pre-coated with Ag
and stabilized in laboratory oven for 1 h at 80
C. Following this, the
synthesized CuO powders were drop casted on the glass substrate
and kept in furnace for 4 h at 150
C. The final prepared specimens
were subjected to NH3 sensing.
The sensing response under the influence of gas is calculated as
the relative change in sensor resistance given by,
203
S ¼ ðR0  RG Þ=RG (1)
where, S e Sensor response, R0 e resistance in air ambience, RG e
electrical resistance under the influence of reducing gas.
3. Results and discussion
Fig. 1 represents the FE-SEM micrographs of (a) undoped CuO
NRs, (b) 2 at.% Cr doped CuO NBs and (c) 6 at.% Cr doped CuO NBs.
From the Fig. 1(a), it can be observed that the undoped CuO formed
well oriented uniform nanorods. As seen from the inset, the
nanorods are having smooth edges with an average diameter of
35 nm and length of 150 nm.
As seen from the Fig. 1(b), on doping with 2 at.% Cr in CuO, the
morphology evolved from the rod-like to boat-like nanostructures
with an average width of 800 nm and length of 1000 nm. However,
when the Cr concentration in CuO was increased further to 6 at.%,
there is no significant change from the boat-like morphology
(Fig. 1(c)) or average length, but the average width increased to
1500 nm.
For a better view of the boat like CuO nanostructures, trans-
mission electron microscopic (TEM) image was obtained for the
6 at.% Cr doped as shown in Fig. 1(d). The particles showed well
defined boat like structures which are symmetrical about its major
axis. It is observed that the longer nanoboats have sharp and nar-
row tips where as shorter ones possessed wide and smoother tips.
However, few random particles showed broken edges as a result of
incomplete growth during synthesis. The inset in Fig. 1(d) shows
the magnified image of a single nanoboat which possessed a length
of 1758 nm and 549 nm. It can be observed that the nanoboat
consists of a thicker core and where as the shell (edges) are thinner
and more transparent. The 2 at.% and 6 at.% Cr doped nanoboats
showed larger size distribution as compared to the narrow size
distribution of the undoped CuO nanorods attributed to the het-
erogeneous nucleation by Cr addition.
From the FE-SEM and TEM microscopic investigations, it is
observed that the morphology of the CuO nanostructures synthe-
sized by hydrothermal process is highly dependent on the reaction
conditions and dopant incorporation. It is interesting to note that Cr
doped samples exhibits rough particle boundaries as compared to
the smooth edges of undoped CuO sample. Cao [12] suggested that
structural defects can efficiently drive the hydrothermal growth
process in crystals. In our case, the small concentration of Cr in-
fluences the nucleation process and also induced structural defects
during the growth process which led to peculiar morphologies in
CuO nanocrystals. It is promising that the incorporation of Cr in
hydrothermally synthesized CuO nanostructures can modify the
morphology and surface area which is much needed as most of the
desirable physical properties in nanomaterials for various applica-
tions such as sensing, catalysis etc. are greatly dependent on these
parameters.
The overall composition of the doped CuO samples was
analyzed by energy dispersive spectroscopy (EDS) and is presented
in Fig. 2. The obtained results are summarized in Table 1.
Fig. 3 shows the XRD patterns of undoped and Cr doped CuO
nanostructures recorded using Cu Ka radiation (l ¼ 1.5418 Å). The
observed diffraction peaks for all the samples were indexed by
comparing with the standard JCPDS data [JCPDS Card No. (5-0661)].
All peaks are well correlated with the monoclinic phase of CuO
reported in literature [8,11] and no impurity peaks were found. As
shown in the inset, the incorporation of Cr in CuO resulted in a
slight shift in the peak positions due to the replacement of Cu atoms
by Cr in the CuO lattice. However, Cr doping did not alter the basic
monoclinic lattice structure of CuO.
204 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208

Fig. 1. FE-SEM images of (a) undoped, (b) 2 at.%, (c) 6 at.% Cr doped CuO, and (d) TEM micrograph of 6 at.% Cr doped CuO nanostructures. Inset shows particles under higher
magnification.

Fig. 2. EDS of (a) 2 at.% and (b) 6 at.% Cr doped CuO NB.

The peak position and full width at half maximum (FWHM) of
the main diffraction peaks along with the calculated lattice pa-
rameters are summarized in Table 2. The least square method
described by Giacovazzo et al. [13] was used in the lattice param-
eter calculation. It is appreciable that doping of Cr influenced
mainly on the growth kinetics and surface energy of the crystalline
Table 1
Elemental composition of doped CuO samples.
Cr dopant concentration (at.%) At.% (EDS average)
Cu O Cr
2 42.92 55.09
6 32.55 63.54
planes thereby altering the morphology, without depreciating the
purity or crystalline quality of the CuO nanostructures.
In order to investigate the energy level transitions and defects,
photoluminescence spectrum was recorded for all the samples by
exciting them with a radiation of wavelength 350 nm. Fig. 4 rep-
resents the room temperature emission spectra along with
Gaussian deconvoluted peaks obtained in the range of 350e610 nm
for (a) undoped (b) 2 at.% and (c) 6 at.% Cr doped CuO samples. All
the three samples exhibited a strong UV emission at around 415 nm
which is attributed to the excitonic/near band edge transition with
the band gap energy of 2.98 eV. The excitation radiation with en-
ergy greater than the band gap energy (2.98 eV) must have resulted
in direct excitement of electron from the valence band to the
1.99 conduction band. This excitation subsequently leads to the forma-
3.91
tion of free pairs of electrons and holes in conduction and valence
 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208 205

bands, respectively. These photo-excited electrons may de-excite to

Fig. 3. XRD pattern of undoped, 2 at.% and 6 at.% Cr doped CuO nanostructures.
their initial states by two competitive ways. They can either relax to
the exciton traps in band gap or subsequently relax further to
valence band by the radiative transitions via trapped exciton re-
combinations or undergo non-radiative transitions [14]. Hence,
the emission spectrum observed in our samples is attributed to the
radiative transitions corresponding to trapped exciton re-
combinations. The relatively weak blue emission observed around
460e497 nm may be due to structural defects such as surface deep
traps. The appearance of a strong peak around 567e569 nm in Cr
doped samples which is not evident in undoped CuO could be
ascribed to the presence of oxygen vacancies. In oxide nano-
materials, the origin of defect related visible emission is generally
asserted to the oxygen vacancies [15]. It is well known that p-type
semiconducting behaviour of CuO should be due to its Cu vacancies.
Recently, it has been theoretically predicted that though Cu va-
cancies are the most prominent defects in CuO, they might not
contribute in any of the emissions discussed above [16]. On the
other hand, oxygen vacancies or OCu anti-site defects are more

Table 2
Peak positions, full width at half maximum and lattice parameters obtained from the XRD and Rietveld analysis.

Cr conc. (at.%) Diffraction peaks Lattice parameters (Å)

(002) (111) a b c

Peak position FWHM Peak position FWHM

0 35.452 0.231 38.686 0.212 4.6504 3.3903 5.0997

2 35.443 0.193 38.694 0.195 4.6837 3.4226 5.1288
6 35.544 0.210 38.799 0.219 4.6700 3.4601 5.1441

Fig. 4. Room temperature PL spectrum of (a) undoped, (b) 2 at.% and (c) 6 at.% Cr doped CuO nanostructures.
206 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208
likely responsible for these emissions since their formation energy
is much closer to that of Cu vacancies.
The electrical properties of the samples were analyzed by a
temperature dependent IeV measurement set-up. Fig. 5 shows the
typical IeV characteristics of the CuO samples measured at
Fig. 5. IeV characteristics of (a) undoped, (b) 2 at.% and (c) 6 at.% Cr doped CuO
nanostructures.
temperatures ranging from RT to 120
C. Ag paste was used as
contact electrode and the output current measurements were
made while the voltage was swept between 6 V and þ6 V. The
straight line IeV plots confirm the established ohmic contact be-
tween the electrodes and the oxide specimen. The average resis-
tance could be calculated from the slope of these lines.
Fig. 6 shows the Arrhenius plot representing the temperature
dependent conductance (i.e. resistance calculated from IeV curve)
of the undoped and Cr doped samples. As expected, the conduc-
tance (C) increases (resistance decreases) with increase in tem-
perature which is a characteristic attribute of semiconductor
materials. The decrease in resistance with temperature is due to the
increase in the conduction electron density at higher temperatures.
In order to understand the activation reaction process which
determines the sensing efficiency of metal oxide sensors at low
temperature, the activation energy was calculated from Arrhenius
plot. The temperature dependent conductance of a semiconductor
material can be represented by the following equation,
C ¼ C0 eðDE=kT Þ (2)
where, C0 is the pre-exponential factor given by,
 . 3=2
C0 ¼ 2emh 2pmh * kT h2 (3)
where the activation energy for the excitation of acceptor atoms is
obtained as, DE ¼ Ec  Ev , m*h & mh are the effective mass and
mobility of holes respectively, Ec & Ev are the energy level values
corresponding to the bottom-edge of the conduction band and the
top edge of the valence band respectively, T is the absolute tem-
perature of the material and k is the Boltzmann constant. The
temperatureeconductance plot in the form of ln (C) versus 1/T can
be drawn according to the following equation,
lnðC Þ ¼ lnðC0 Þ þ DE=2kT (4)
Using the above equations, the activation energy is calculated as
2.25, 2.14 and 1.84 eV for undoped, 2 at.% and 6 at% Cr doped CuO
nanostructures, respectively. The reduction in activation energy is
observed with increase of dopant concentration due to the creation
of more number of oxygen vacancies by Cr incorporation in CuO.
Higher the oxygen vacancies, less will be the activation energy
which concurs with the deep level emission observed in doped
samples from PL emission spectra [15].
Fig. 6. Arrhenius plot of ln C versus inverse of operating temperature (1/T).
 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208
Fig. 7. Temperature dependent ammonia gas sensing response of undoped, 2 at.% and
6 at.% Cr doped CuO. Inset shows the variation in resistance of the samples with
temperature.
Gas sensing, based on CuO nanostructures is realized by the
catalytic response of the metal oxide to specific gaseous stimulus
which is measured as a change in resistance of the specimen. In fact
it is the surface conductivity of CuO which makes it a potential
candidate for semiconductor resistive gas sensor applications.
All the CuO samples were subjected to ammonia sensing mea-
surements at various temperatures ranging from ambient to 120
C.
Fig. 7 shows the variation of the NH3 sensing response of undoped
and Cr doped CuO samples as a function of temperature under at-
mospheric air and gaseous conditions. The inset in Fig. 7 shows the
change in resistance as a function of temperature under atmo-
spheric conditions. It is observed that the resistance decreases
exponentially with the increase in temperature which is a charac-
teristic feature of a p-type semiconductor having holes as majority
charge carriers [10]. The decrease in resistance with increase in
temperature is accounted for the thermal generation of free holes
in semiconductors.
The Arrhenius behavior of these parameters has been already
discussed in Fig. 6.
The sensor responses at RT were found as 20.50%, 22.33% and
30.58% for the undoped, 2 at.% and 6 at.% Cr doped CuO samples
respectively. It is observed that the relative change in resistance
showed a Gaussian trend and thereby sensor response showed a
maximum for 75
C considering the doping concentration, 6 at.% Cr
doped CuO exhibited the highest sensing response with a featured
magnitude of 180% at 75
C.
Sensing response of the CuO samples was also measured as a
function of NH3 concentration and the results obtained at RT are
shown in Fig. 8(a). All the three samples showed significant
response to NH3 even for very low concentrations at RT. It is
observed that the sensor response increased with increase in
concentration from 100 to 600 ppm by following power law [17]
which is given below,
S ¼ AC a
logðSÞ ¼ A0 þ a logðCÞ
where S is the sensing response, C the concentration of NH3, A is the
proportionality constant and a is the power law exponent. a can be
determined from the fit of so called logelog plot with log(C) along x
axis and log(S) along y axis which is represented in Fig. 8(b). From
207
Fig. 8. (a) Influence of ammonia concentration on the gas sensing response of undo-
ped, 2 at.% and 6 at.% Cr doped CuO and (b) logelog plot to determine a.
the fit, values of a are obtained as 0.7, 1.03 and 1.05 for the undoped,
2 at.% and 6 at.% Cr doped samples respectively. The power law
dependence arises from receptor and transducer functions, i.e., the
adsorption and interaction of reducing gas molecules with the
surface of the metal oxide and the subsequent change in surface
potential [18]. The electronic interaction between Cr and CuO fa-
cilitates gas sensing through the change in electrical resistance. In
normal atmosphere, the formation of oxygen adsorbates (O/O2)
on the surface of CuO NRs and Cr doped CuO NBs results in the
formation of electron-depletion surface layer due to the electron
transfer from NRs/NBs to oxygen. However, target gas molecules
(NH3 in this case) interact with the adsorbate and free the electron
into the sensor matrix. It is clear that the sensor response increases
with the dopant concentration. The comparatively better response
observed for 6 at.% Cr doped CuO nanoboats may be ascribed to the
oxygen vacancies/anti-sites present in the sample.
Apart from these, it is found that the resistance of Cr doped CuO
varies as a function of Cr/(Cr þ Cu) ratio. Comparing with undoped
CuO, the increase in resistance of 2 at.% Cr doped CuO sample may
be ascribed to the incorporation of Cr in CuO matrix. The substi-
tution of Cu2þ by Cr2þ introduces a hole since Cr acts as an acceptor
impurity. The resistance increases as a result of increase of free
charge carrier concentration (holes of CuO). When the ratio of Cr/
(Cr þ Cu) increases from 2 at.% to 6 at.%, the resistance of Cr doped
CuO decreases. It is speculate that the oxygen vacancy which acts as
donor impurity plays a dominant role in the conductivity of CuO
[19,20]. Similar behavior was observed by Jinjin et al. [21] on Al
doping in SnO2 lattice which enhanced the sensing response of
208 S. Bhuvaneshwari, N. Gopalakrishnan / Journal of Alloys and Compounds 654 (2016) 202e208
SnO2 by introducing oxygen vacancies. The increase in oxygen va-
cancies in the case of Cr doped CuO nanostructures is substantiated
by the green emission observed in PL spectra. This facilitates higher
absorption of oxygen which in turn increases the interaction of
sensor material with the reducing gas and thereby enhancing the
sensor response.
4. Summary and conclusions
In summary, undoped, 2 at.% Cr and 6 at.% Cr doped CuO
nanostructures were synthesized by a simple hydrothermal
method. FE-SEM and TEM microscopic investigations revealed that
undoped CuO formed well defined nanorods which evolved to
nanoboats upon Cr addition. XRD analysis revealed that no sec-
ondary phases are present indicating the phase purity of the
sample. In PL emission spectra, a strong green emission at 566 nm
validates the increase in oxygen vacancies which in turn boost the
sensing response by adsorbing more surface oxygen. The increase
in oxygen vacancies also reduces the activation energy that facili-
tates the sensor device to respond at low temperatures. From the
temperature dependent sensing measurements, it is found that for
all samples, the sensing response increases with temperature up to
75
C beyond which decreases due to the desorption of oxygen at
the sensor surface. At room temperature, the sensor response was
found to have a power law dependent relation with the gas con-
centration. Among the three CuO samples, 6 at.% Cr doped CuO
nanoboats showed better NH3 sensitivity which is attributed to the
higher specific area at the surface and oxygen vacancies which is
not evident in undoped CuO nanorods.
Acknowledgment
One of the authors S. Bhuvaneshwari is thankful to the funding
agency, DST, Govt. of India for offering the INSPIRE fellowship
(DST/INSPIRE Fellowship/2012/647) to carry out this research work.
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