Sensors and Actuators B 231 (2016) 474–483

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Highly sensitive wireless H2 S gas sensors at room temperature based

on CuO-SWCNT hybrid nanomaterials
Mohsen Asad a,b,∗ , Mohammad Hossein Sheikhi a
a
Semiconductor Device Research Center, School of Electrical and Computer Engineering, Shiraz University, Shiraz 71345-1585, Iran
b
Department of Electrical and Computer Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1, Canada

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

Article history: Detection of H2 S in very low concentrations with innovative functional materials is of key importance
Received 12 November 2015 in oil and gas industries. One approach to control the limit of detection for gas sensors is to engineer
Received in revised form 11 February 2016 the shape of sensing nanostructures to develop high performance gas sensors. By controlling the pro-
Accepted 7 March 2016
cess parameters in synthesizing of CuO nanostructures, programming the limit of detection has been
Available online 8 March 2016
obtained up to 100 ppb H2 S for CuO-SWCNT nanostructures at room temperature. Gas sensing evalua-
tion of nanomaterials indicates the role of surface to volume ratio on the performance of the sensors.
Keywords:
The crystalline structure, chemical composition and morphological characterization have been studied
RFID tag sensor
H2 S gas sensing
by X-ray diffraction, Furrier transform IR spectroscopy, Raman spectroscopy and field emission scanning
CuO-SWCNT electron microscopy. The CuO-SWCNT nanomaterials has been immobilized on top-side of commer-
Programing limit of detection cial 13.56 MHz radio frequency identification (RFID) tag by drop-casting to produce tag sensors. Due to
change in radar cross section of the fabricated wireless devices, a reduction of reflectance and shift of
peak frequency toward lower values is observed by increasing the gas concentration. Repeatability and
long life-time (30 days) of fabricated sensors indicate their effective potential for remote healthcare and
environmental monitoring applications.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
H2 S is one of the toxic gases which is widely produced in oil
and gas industries. It is flammable, explosive and risky to environ-
ment (like acidic rain) and human once any leakage takes place
at the industrial sites. It can be detected by human nose at con-
centrations above 0.13 ppm and has a rotten egg odor. Long-term
(10 min) exposure to H2 S has adverse effects on the smelling and
nerve system and causes inhibiting cell respiration by enzymes in
bloodstream. Repeated exposure to H2 S could be fatal and thus it
is crucial to detect it at low concentrations.
Since nanostructure materials possess uniform morphologies,
small size and narrow distribution, they usually exhibit strong
quantum confinement effect and unique electrical, optical, mag-
netic and catalytic properties [1–3]. Today, nanostructures based on
self-assembly of metal oxides (MOx) have been widely used for gas
sensing applications [4]. While, weak interaction (van der Waals or
hydrogen bonds) bonded building blocks of nanostructures [5], to
obtain a strong bonding and efficient chemical interaction between
∗ Corresponding author.
E-mail address: mohsenasad@shirazu.ac.ir (M. Asad).
them, the covalent coupling has been induced [6]. Numerous MOx
based nanostructures have been used in direct or indirect detection
of dangerous gases [7–10]. In direct gas detection by nanostruc-
tures, MOx architectures are grown directly on the substrate and
interact by gas molecules directly [11–13]; while for indirect gas
detection, changes in electrical or optical properties of MOx have
been measured by secondary materials or systems [14,15]. Because
of high surface to volume ratio of hierarchical structures, they
showed stronger response towards chemical agent compared to
the pristine structures. Some typical examples of them are hol-
low porous spheres [16,17], specific structure via pyrolysis of
precursors [18,19], branched catalysis [20,21], hierarchical hybrid
structures [22], opal inverse film [23], nanotrees/forest [24] and
multilayer nanowire [25].
Copper oxide (CuO) is a well-known metal oxide with efficient
catalytic activity [26], unique electrochemical characteristics [27]
and excellent adsorption properties [28]. Interesting gas sensing
properties have been reported for p-type CuO semiconductors [29].
Enhanced oxygen adsorption capabilities and large surface area,
make CuO as a promising candidate for gas sensing applications
[30]. In particular, our group has introduced Cu based nanos-
tructures as promising building blocks for enhanced gas sensing
towards H2 S [31]. Moreover, Meng et al. used CuO microspheres

http://dx.doi.org/10.1016/j.snb.2016.03.021
0925-4005/© 2016 Elsevier B.V. All rights reserved.
 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483 475

for ppb detection of H2 S [32]. Hierarchical hollow CuO prepared by jugated to the flower-shaped CuO to provide an effective charge
Qin et al. exhibited an acceptable response under exposure to H2 S transfer channel between CuO nanostructures and electrodes. We
[33]. integrated the flower-shaped CuO-SWCNT into the conventional
One approach to control the limit of detection for gas sen- RFID tags to cause change in resistance that results in a shift in
sors is to govern the shape of sensing nanostructures. This is output frequency and changes the reflected power.
due to their morphology dependent properties, which require
high surface to volume ratio. Considering H2 S gas sensing prop-
2. Experimental
erties of CuO nanostructures, they have been developed by
various physical and chemical routs [34]. Hydrothermal process
2.1. Material preparation and characterization
in ethanol-water solution has been used by Liu et al. to pro-
duce nanoribbon-assembled CuO dandelions [35]. For reducing the
CuO-SWCNT samples with different morphologies of flower-
time of hydrothermal process and preparing large scale of CuO
shaped CuO nanostructures were hydrothermally prepared by
nanostructures, microwave assisted processes are introduced by
using Cu(NO3 )2 as copper precursor in deionized (DI) water at dif-
Volanti et al. [36]. Xu et al. has shown controlling the size of CuO
ferent temperatures from 130 ◦ C to 150 ◦ C and one sample with
microspheres by adjusting the amount of NaOH in tartaric acid-
an additional step in 150 ◦ C. Typically, 60 mg of Cu(NO3 )2 was
assisted hydrothermal process [37]. Furthermore, Vaseem et al.
dissolved in 50 mL DI water with stirring for 30 min at room tem-
prepared flower-shaped CuO by hexamethylenetetramine assisted
perature. Later, 5 mg NaBH4 as a reducing agent was added to the
low temperature hydrothermal route [38]. Recently, two phase
solution following with 15 min stirring. Then, the solution was
morphology of CuO nanostructures have been prepared by using
transferred into a Teflon-lined autoclave and the pH level of the
Cu(CH3 COO)2 /urea and Cu(NO3 )2 /urea solution in hydrothermal
solution was kept at 2–3 using HCl. The autoclave was then sealed
process [26]. However, using these nanostructures in robust sensor
and heated at several temperatures of 130 ◦ C–150 ◦ C, separately, in
architecture is a dilemma yet and synthesizing CuO nanostructures
an oven without any temperature ramp control. After 3 h, the solu-
using these methods are limited to thin film sensors produced by
tion was removed from Teflon-lined autoclave, and washed several
spin coating.
times with pure DMF to reach pH 7. Then, using centrifuge process
Furthermore, using CuO-single wall carbon nanotube (SWCNT)
at 6000 rpm the CuO nanostructures were collected and transferred
nanostructures offers advantages of both systems including high
to 100 mL DMF solution. To control the architecture and pattern of
surface to volume ratio, effective pathway for electron transport by
the building components of the sensors and consequently program-
SWCNT [39], enhanced and tunable surface reactivity implying pos-
ming the limit of its detection, self-assembly of CuO nanostructure
sible room-temperature operation, faster response and recovery
was repeated by a second step of CuO growth on previous obtained
time, ease of fabrication and manipulation and low power con-
materials at 150 ◦ C (we name this sample re-150 ◦ C). Consequently,
sumption. However, some problems are associated with the use of
20 mg of produced CuO powder was dissolved in DI water and later
nanomaterials such as sample to sample variation, and the in-built
5 mg of Cu(NO3 )2 was added followed by Teflon-lined autoclave
issue of randomness which raise a major concern over the impor-
process, at the same temperature as previous process for another
tant parameters, namely reproducibility and repeatability of the
3 h. Finally, to prepare efficient carrier transfer channel between
sensors. Previously, to overcome the reproducibility problem, use
CuO and device electrodes, 20 mg of functionalized SWCNT was
of nanomaterials in thin film form has been suggested to measure
added and the solution stirred at 100 ◦ C for 30 min. The flower-
the average properties of multiple nanostructures [40].
shaped CuO-SWCNT nanostructures were obtained after several
The integration of nanoscale chemical sensors with wireless
washing of the solution with ethanol and filtration by PTFE mem-
device is an approach to improve device applications in per-
brane (with 0.45 ␮m pore).
sonal healthcare, environmental monitoring and chemical agent
The morphology of the various flower shaped CuO-SWCNT
detection [41–46]. In addition, integrating chemical sensors into
nanomaterials were studied using field emission scanning elec-
wireless communication networks (contactless chemical sensors)
tron microscopy (FE-SEM, model Hitachi S4160). X-ray powder
has particular advantages including low-cost installation, sensing
diffraction (XRD Philips XPert Pro Model) with illumination source
dangerous chemicals in the local environment and capability of
with a wavelength of  = 1.54 nm at 2 angels between 10◦ and
internet of things (IOT). Passive RFID tags are read by RFID tag
90◦ has been used to study the phase purity of the flower shaped
readers, when a radio-frequency carrier signal illuminates on the
CuO-SWCNT final nanomaterial. For investigating the chemical
passive RFID tag antenna and an AC voltage creates based on elec-
composition of hybrid materials, Fourier transform infrared (FTIR)
tromagnetic coupling. A standard IC chip converts signals to a DC
spectra was collected using a Nicolet Magna IR 550 spectrometer.
current to supply other operation of microchip. This remarkable
Raman spectra has been recorded at room temperature by stan-
property of wireless sensors provides remote sensing without using
dard backscattering geometry using a high power laser diode with
a power source, makes them a unique candidate in wearable sen-
excitation wavelength of 785 nm and supplying power of 50 mW.
sors for healthcare controlling (a practical approach is presented in
Fig. S1, Supplementary information).
Recently, our group has reported SWCNT decorated with Cu 2.2. Gas sensing properties of CuO-SWCNT
nanoparticles as a promising material for high sensitive and flexi-
ble H2 S gas sensors [47]. Following the strategy used by Soleymani The gas sensing properties of flower shaped CuO-SWCNT hybrid
et al. [48] to program the detection limit of biosensors by con- nanomaterials have been measured for each morphology using two
trolling the process of electroplating of metallic nanostructures, gold (Au) interdigitated array (IDA) electrodes (deposited by ther-
the synthesis of CuO nanostructures with different morphologies mal evaporator system, Yar Nikan Saleh Co., Iran). 5 mg of each
with application in gas sensing is presented. 3D flower-shaped CuO-SWCNT nanomaterials was dispersed in 50 ml of DMF sepa-
CuO nanostructures have been prepared by using of Cu(NO3 )2 as rately and each solution was sonicated 10 min at room temperature.
precursor. By adjusting the process parameters such as tempera- The solution has been drop-casted on the IDAs and the hybrid nano-
ture, controllable structures obtained. A two-step process has also material spin coated at 500 rpm for 30 s to obtain a thin film on
been designed to synthesize branches on the flower-shaped nanos- the surface. The devices annealed at 90 ◦ C in an inert atmosphere
tructures for improving and controlling the gas sensing properties for 30 min to obtain a good ohmic contact between CuO-SWCNT
of fabricated sensors. Functionalized SWCNT has been used con- and electrodes. The current-voltage characteristics of each sample
476 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483
was measured with HP4145 semiconductor parameter analyzer to
ensure about the ohmic properties of devices.
The devices have been placed in a vacuum chamber and the
changes in the resistance, under exposure to gas, were measured
using HP4145 connected to a computer. The fabricated devices
were exposed to various H2 S gas concentrations (100 ppb–50 ppm)
by a mass flow controller and air was used as the background. When
the resistance of the device was remained consistent upon expo-
sure to H2 S gas, the compressed air has been introduced into the
chamber to remove the H2 S gas molecules and recover response to
the initial value.
The reliability of the fabricated sensors have been evaluated
under exposure to 1 ppm H2 S gas. The long-term evaluation of the
CuO-SWCNT based devices has also been carried out under expo-
sure of 1 ppm H2 S during a period of 30 days. Each measurement
performed every 3 days after purging process with Ar for 30 min to
eliminate any unwanted molecules in the interior of the chamber.
The response time of the fabricated sensors with re-150 ◦ C flower-
shaped CuO-SWCNT at 100 ppb H2 S has also been measured to
compare the results with previous published papers.
2.3. Wireless sensor fabrication and characterization:
To construct the sensor on the RFID tag, one of the commercial
13.56 MHz RFID tag with a flexible substrate has been used with
EM4034 standard IC (Fig. 1a). As shown in Fig. 1b, the antenna is
mounted on the topside of the tag with an adhesive paste on the
backside to attach it on the body skin. The connection between
topside antenna and the main structure is constructed with a via-
like junctions. To deposit the sensing nanomaterials on the tag, the
top side of it was covered with commercial adhesive tape except
the antenna surface to protect unwanted surface of the tag from
chemical treatment. Then, flower-shaped CuO-SWCNT materials,
obtained in separate temperatures, were dispersed in DMF, and
then drop-casted onto the topside antenna and heated at 80 ◦ C for
2 min to obtain a good contact with antenna. The adhesive tape
was then removed from the surface and RFID tag was inserted in
an oven at 50 ◦ C for 5 min to evaporate the solvent and prepare a
good contact between sensitive materials and antenna (Fig. 1c). The
fabricated wireless sensor has been attached to the skin of the hand
for further demonstration in healthcare monitoring (Fig. 1d).
The fabricated wireless sensors were exposed to different con-
centrations of H2 S (100 ppb and 200 ppb) at room temperature by
placing the RFID sensor in a test chamber. Different concentrations
of H2 S were injected into the chamber using a computer-controlled
MFC (MKS Instrument) using air as background gas. The RFID tag
radio-wave reflectance corresponded to backscattering between
the sensors and RFID reader was collected over the range of inter-
est with a general purpose network analyzer (Agilent HPE8361A) as
the RFID tag sensor array was exposed to H2 S gas. The RFID reader
antenna was positioned at 5 cm distance from the tag sensors, and
each tag was evaluated individually.
3. Results and discussions
3.1. Morphology and structural analysis
A thorough understanding of the CuO formation mechanism is
highly desirable to be able to control its chemical properties and
morphology. The FE-SEM image (see Fig. 2) were taken from the
samples obtained from hydrothermal synthesis in various tem-
perature of 130 ◦ C–150 ◦ C, where is possible to observe final CuO
nanostructures obtained in several growth temperatures. Fig. 2a
shows an image of the first sample of the CuO with flower-like
morphology after 3 h growth at 130 ◦ C. While Cu ions were pro-
duced in DI water solution, the primary CuO nanocrystals formed
with a core composed of smaller particles. It is proposed that the
cross-shaped microcrystals have an active center for heteroge-
neous nucleation. According to Fig. 2b, by random aggregation of
CuO that produced polycrystalline nanostructures, they are likely
to form triangular cross-like plates with a same core point. The
growth process continues to form 3D open structures at 150 ◦ C,
shown in Fig. 2c. This proposes that cross extremities are composed
of imperfectly alignment blocks which could serve as the substrate
for the subsequent heterogeneous nucleation. As shown in Fig. 2d,
formation of final morphology consists of complete flower-like
CuO nanostructures with additional branches. Formation of CuO
nano-branch came from additional Cu complex ions in the solu-
tion and proposed self-assembly of CuO nanostructures on lower
energy surfaces (three-order structures) as an efficient way to con-
trol the architecture and morphology of the final nano materials.
The growth mechanism is similar to those of the branched ZnO [49]
and Cu2 O crystals [50].
All four specimens were identified by X-ray powder diffraction
(XRD) to study the phase purity of the final products, as shown
in Fig. 2e–h. The XRD results show that all of the CuO nanos-
tructures are crystalline where additional peaks originate from
SWCNT and no impurity peaks observed. All peaks in diffractogram
can be indexed by the tenorite phase of CuO with a monolithic
structure (JCDP 481548; a = 4.6883 A, b = 3.4229 A, c = 5.1319 A, and
ˇ = 99.506◦ ). The labels above peaks in Fig. 2h are the respective
(hkl) indices. As shown in Fig. 2e–h, different relative peak intensi-
ties for each sample are compatible with the formation of crystals of
different dimensions; i.e., lower intensity peaks for step 1 as com-
pared to step 4 (branched flower-like nanostructures). The patterns
of SWCNTs are revealed in all XRD spectra. This patterns show peaks
of (100) and (002) which are related to the graphite phase (NO 41-
1487, JCPDS card file). These results show the high phase purity and
crystallinity of the CuO-SWCNT prepared by hydrothermal process.
3.2. FTIR and Raman spectroscopy
Previous theoretical and experimental results showed that six
IR adsorption sites of CuO are located at 147, 161, 321, 478, 530
and 590 cm−1 [51–55]. The FTIR transmission spectrum of flower-
shaped CuO-SWCNT (re-150 ◦ C) is presented at Fig. 3a. For CuO,
three main infrared peaks are observed at 165, 330 and 615 cm−1
which are correspond to the Au, Bu and Bu’s vibrational modes of
monoclinic phase CuO (space group C2/c), respectively [56,57]. The
change in anisotropic crystal orientation of CuO at re-150 ◦ C sample
causes these shifts in infrared peaks that −as will be seen- plays a
critical role in effective gas adsorption of programmed nanostruc-
ture. Moreover, mode due to Cu2 O is not seen in the spectrum at
147 cm−1 , which is completely in agreement with the XRD pat-
tern of CuO, exhibiting monoclinic phase of CuO nanostructures.
The peak at 2360 cm−1 belongs to CO2 and came from environ-
ment of the tablet made with KBr. Spectrum also demonstrates the
peaks corresponding to hybridized vibrant mode of C C of sp2 at
1620 cm−1 .
Flower-shaped CuO-SWCNTs (re-150 ◦ C) synthesized in this
study are also characterized using Raman spectroscopy in order to
determine the phase and chemical structures. Fig. 3b illustrates the
Raman scattering spectrum of CuO-SWCNT sample from re-150 ◦ C.
The well-known peaks of SWCNT are G and D bands, correspond-
ing to the Raman active modes of graphite around 1582 cm−1 and
1350 cm−1 , respectively [58]. The G band is originated from the E2 g
phonons of sp2 states and the D band is originated from the A1 g
symmetry. The radial breathing modes (RBM) are distinguishable
in the low frequency region of the spectrum.
The CuO phase belongs to the C2h 6 space group. This space group
with two molecules per primitive cell, consists of the zone cen-
 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483
Fig. 1. (a) The commercial 13.56 MHz RFID tag which has been used in this work to fabricate wireless sensors. The standard EM4034 IC was implemented in this tag as AC
to DC convertor and standard CMOS circuit. (b) Topside of the used tag. Clearly, the topside antenna is connected to the main structures of the tag by via-like junctions. (c)
The fabricated wireless sensor after deposition of flower-shaped CuO-SWCNT sensing material on it. (d) A practical demonstration of the application of fabricates wireless
sensors for healthcare monitoring or environmental observing.
ter Raman active normal modes RA = 4Au + 5Bu + Ag + 2Bg; three
acoustic modes (Au + 2Bu), six infrared active modes (3Au + 3Bu),
and three Raman active modes (Ag + 2Bg) [59]. As shown in Fig. 3b,
the Raman active optical phonon has been observed at 330 cm−1
which proves the formation of only CuO monoclinic phase and is
consistent with results from FTIR spectroscopy and XRD. Our results
are also consistent with the previous reports on hydrothermal for-
mation of CuO [60].
3.3. Gas sensing evaluation
The electrical properties of flower shaped CuO-SWCNT was
investigated using an IDA based configuration composed of 10 ␮m
width and 200 ␮m length gold fingers, totaling 25 pair fingers
(Fig. 4a). The prepared nanomaterials were dissolved in DMF and
spin-coated on the IDAs (Fig. 4b). The electrical conductance of
the samples was evaluated by measuring the current-voltage (I–V)
characteristics of them over the voltage range of −0.1 V–0.1 V, as
shown in Fig. 5a. All devices showed linear I–V characteristics in
the suggested range which confirms the ohmic electrical contact
with electrodes. The conductance of the devices was increased
by increasing the synthesizing process temperature. The re-150 ◦ C
sample has the highest conductance among all devices. This con-
firms our previous postulation in describing the growth mechanism
and programing the nanostructures that increase in the tem-
perature will enhance the formation of nano-plates and further
self-assemble towards flower-like structure. The excess Cu ions in
re-150 ◦ C process also attached to the primary nanocrystals by the
selective adsorption on the low energy sites on the crystal surface.
477
This enhanced conductance is attributed to the higher concentra-
tion of CuO in the final nanomaterials.
The unique catalysis properties of Cu NPs over SWCNTs have
been investigated in our previous report [47] by using density func-
tional theory (DFT). As we showed previously, exposure of Cu NPs
decorated SWCNTs to H2 S leads to dissociation of H2 S to H2 and
formation of CuS. Beside, SWCNT has a great affinity towards H2
adatoms and this causes change in transport properties of them as
an ideal carrier transport channel.
In this work, the gas sensing properties of as-prepared flower
shaped CuO-SWCNT sensitive nanostructures have been measured
toward very low to relatively high concentrations of H2 S from
100 ppb to 50 ppm. Fig. 5b presents the sensor sensitivity with
the different CuO morphologies as a function of gas concentration
versus time. The sensor sensitivity,R (%), was calculated using the
relation:
Rg − Ra
R (%) = | | × 100 (1)
Ra
where, Ra and Rg are sensor’s resistance in air and test gas
condition, respectively [47]. Noticeably, for a low gas concentra-
tion of 100 ppb the response is reversible and the base resistance
remains constant. The sensing mechanism of CuO-SWCNT is shown
schematically in Fig. 6. Two main reactions on the surface of the CuO
were introduced by Ramgir et al. [61] as below:
2H 2 S(g) + 3O−
2(ads)
→ 2H22 O(g) + 2SO2(g) + 3e− (2)
H2 S(g) + CuO(s) → CuO(s) + H2 O(g) (3)
Cu vacancies in CuO make it a p-type semiconductor, as pre-
viously reported by Bardeen et al. [62]. Adsorption of oxygen from
478 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483

Fig. 2. (a) FE-SEM image of the nanostructured CuO-SWCNT synthesized at 130 ◦ C, (b) 140 ◦ C, (c) 150 ◦ C, (d) re-150 ◦ C. (e)–(g) XRD pattern of the synthesized CuO-SWCNT
at 130 ◦ C, 140 ◦ C, 150 ◦ C, re-150 ◦ C, respectively.
 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483
Fig. 3. (a) FTIR spectra recorded for nanostructured CuO-SWCNT obtained from re-150 ◦ C process, (b) Raman spectra of the CuO-SWCNT sample obtained from second 150 ◦ C
process.
Fig. 4. (a) Gold interdigitated array (IDA) fabricated on SiO2 /Si. (b) Fabricated device after spin coating of CuO-SWCNT sensitive film on IDA.
ambient at the room temperature creates surface states [63], which
permit electrons to move from valance band to the conduction band
and remained holes enhance the p-type characteristics of the CuO,
especially in the cross-section of nano-plates in flower-like struc-
ture. At low concentration of H2 S, the gas molecules interact with
the oxygen adatoms on the surface of the CuO according to Eq. (2),
and transfer of released electrons toward SWCNTs leads to recom-
bination with the holes in p-type SWCNT, resulting in an increase
in the resistance of the sensing materials. Adsorbing the released
electrons toward SWCNT is more competitive compared to p-type
CuO because of the lower work function of the CuO compared with
that of SWCNT. This could be the reason of fast response of the fab-
ricated sensor, as shown in Fig. 5c. Obviously, the gas sensitivity
of the nanostructures has direct relation with the effective surface
interaction with the gas molecules. This could explain the higher
sensitivity of the re-150 ◦ C, in comparison with 130 ◦ C and other
nanostructures. This also points out the importance of the program-
ing of the nanostructure synthesis to control the limit of detection
in nanosensors with different morphologies.
It is well known that the linearity in the sensitivity is attributed
to the number of oxygen adatoms consumed per H2 S molecules.
As shown in Fig. 5d, the linearity of sensitivity decreased at high
concentration of the H2 S. For higher concentration of the H2 S, the
chemical reaction take places according to the Eq. (3) on the surface
of the CuO. The formation of metallic CuS layer on the surface of the
CuO prevent H2 S molecules to diffuse toward and interact with the
surface of the CuO. The reduction in diffusion of gas molecules in
479
the nanostructure surface, decreases the linearity of the response.
Formation of CuS layer could also explain the high recovery time of
28 s (see Fig. 5c).
Dynamic sensing measurement of the CuO-SWCNT sensors was
performed under exposure to 1 ppm H2 S at room temperature
to evaluate the reproducibility of the fabricated sensors. Fig. 5e
presents the repeatability and stability of the sensors in presence
of 1 ppm H2 S. It can be found that the initial response and recovery
of the sensors are reliable upon seven successive cycles. In addi-
tion, the long-term response of the sensors was evaluated in a
period of 30 days under exposure of 1 ppm H2 S at room temper-
ature, as shown in Fig. 5f. Each measurement was performed every
3 days after purging the test chamber with Ar for 30 min. A slight
decrease and increase in the response can be attributed to the unde-
sired impurities in the chamber. These results indicate the stable
response of the fabricated sensors at a low concentration of 1 ppm
H2 S.
The response time of fabricated sensors (7 s) is faster than 10 s
reported by Ragmir et al. [64] and 60 s reported by Kuar et al. [65] for
detection of 10 ppm H2 S gas. The recorded limit of detection (LOD)
for fabricated devices (100 ppb) is as small as lower reported LOD
till now (3 ppb) [66] and also explains more sensitivity compared to
results obtained by Kuar et al. (200 ppb) [65]. This high sensitivity
can be attributed to unique chemical interaction of CuO structures
with CuO and high surface to ratio of final sensing materials (re-
150).
480 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483

Fig. 5. (a) I-V characteristics for the CuO-SWCNTs nanostructures prepared at different temperature of 130 ◦ C, 140 ◦ C, 150 ◦ C, re-150 ◦ C which deposited on IDA electrodes,
(b) the gas sensitivity of the different samples exposing to various concentrations of H2 S gas, (c) response and recovery times of the fabricated sensor based on re-150 ◦ C
nanostructures under exposure to 1 ppm H2 S have been obtained 7 s and 28 s respectively. (d) calibration curve of the fabricated sensors based on various nanostructures.
The higher response of the re–150 ◦ C sample is obvious compared to other ones due to higher surface to volume ratio, (e) dynamic response of the fabricated sensors
under exposure to 1 ppm H2 S, which shows the reproducible response in 7 cycles, (f) long-term evaluation of the sensor’s response under exposure to 1 ppm gas at room
temperature.

3.4. Measuring RFID tag response characteristics
Fabricated wireless sensor tags based on re-150 ◦ C sample, have
been characterized in a wireless gas sensing system under expo-
sure to various concentration of H2 S. The radio wave reflected from
RFID tag was collected using network analyzer. Fig. 7a present the
power of the reflected radio wave (S, in dB) versus frequency for
re-150 ◦ C sample under exposure to 100 ppb and 200 ppb H2 S. The
RFID tag has been characterized without exposure to H2 S which
shows larger reflectance, as shown in Fig. 7a. The reflected radio
waves have a relative relation with radar cross section (RCS) of the
RFID tag. When the RFID tag is not exposed to H2 S, the impedance
of the IC chip and RFID antenna is matched and reflection of radio
waves is greater than others. Upon exposing the RFID tag to H2 S,
the released electrons transfer to p-type SWCNT which causes an
increase in the resistance of the RFID tag. The increase of RFID
tag antenna resistance cause impedance mismatching between the
tag antenna and IC chip and as a result, a decrease in the num-
ber of reflected radio waves and a shift in peak frequency toward
lower frequencies, compared to sample without H2 S exposure were
observed (see Fig. 7a). This increase in the resistance due to elec-
tron transfer toward SWCNT is consistent with the results obtained
with IDA structures (see Fig. 5b).
Fig. 7b shows the calibration curve of the sensors as a function of
H2 S gas concentration, where S and S0 are reflectance of the sensor
after and before exposing to H2 S, respectively. The resistance of the
RFID tag antenna increased as the concentration of H2 S increased,
which caused a decrease in normalized reflectance. By considering
the effective interaction of re-150 ◦ C sample with gas molecules
due to higher surface to volume ratio, further increase in resistance
has been obtained resulting in an increase in mismatching between
RFID antenna and IC chip. Because the impedance between antenna
and chip becomes more mismatched in re-150 ◦ C sample, further
decrease in reflected power is perceptible. Additionally, decreasing
the S/S0 at higher 500 ppb H2 S in re-150 ◦ C sample indicated a trend
toward saturation of RFID tag sensors at higher concentration.
In order to investigate the flexible properties of fabricated gas
sensors, we also measured the response of sensors under exposure
 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483 481

Fig. 6. Schematic of the sensing mechanism of fabricated CuO-SWCNT gas sensors were exposed to H2 S. Before exposing to H2 S, surface states have been formed on the
CuO branch-like nanostructures by adsorbing oxygen from environment (as shown in blue color in the figure and named as 3O2 − (ads) ). As H2 S gas reach to the surface of
the nanostructures, gas molecule interacts with the oxygen species (O2 − ) and released electrons go towards CNTs due to high electron affinity of the SWCNTs, as shown at
upper section of the figure by Eq. (1). This cause an increase in resistance of p-type SWCNTs. At higher concentration of gas, in addition to H2 S oxidation, chemical reaction
between H2 S and CuO cause formation of CuS layer (as shown at lower section of the figure by Eq. (2) (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.).

Fig. 7. (a) Change in the reflectance properties of RFID tag sensor based on re-150 ◦ C sample under exposure to 100 ppb and 200 ppb H2 S. The reflectance of the fabricated
sensor is also presented to compare with other ones. As shown by arrays in the figure, by increasing the gas concentration in the chamber, peak frequencies shift towards
lower frequency and reflected power has been reduced simultaneously. (b) Calibration curve of the fabricated sensors versus various concentrations of H2 S for based on
CuO-SWCNT nano-materials versus various concentrations of H2 S. (c) The normalized peak frequency shift as a function of bending radius. The sensors acceptable response
in bending radius larger than 6 mm. (d) Selectivity histogram of fabricated gas sensor under exposure of various gases including 1 ppm H2 S, 100 ppm, CH4 , 100 ppm H2 ,
100 ppm CO and 100 ppm acetone.

of 100 ppb gas as a function of various bending radius. In the ini-
tial test and after bending, the resistance of the sensitive films was
monitored. The change in the sensor’s resistance was negligible.
Fig. 7c shows the normalized peak frequency shift (NPFS) of the
sensor’s response with various bending radius in room tempera-
ture. The sensor shows acceptable response in bending radius larger
than 6 mm. By reducing the bending reduce smaller than 6 mm, the
peak frequency turned toward 13.56 MHz. This can be attributed to
detachment of sensitive film from RFID tag. This problem can be
unravelled by firm assembling of sensitive film by using adhesive
conductive polymers.
Fig. 7d shows the selectivity of the fabricated sensors based
on Cu-SWCNT toward various gases such as 1 ppm H2 S, 100 ppm,
CH4 , 100 ppm H2 , 100 ppm CO and 100 ppm acetone. The reflected
power has been measured as a function of various gas concen-
trations at room temperature. According to selectivity histogram,
the sensor is highly selective towards H2 S and exhibited negligible
response towards other interferences gases. This high selectivity
could be attributed to the unique interaction of CuO nanostructures
with H2 S molecules. A declining response towards H2 is attributed
to adsorption of H2 molecules to SWCNTs which is an accepted
phenomenon.
482 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483
When the RFID tag exposed to H2 S, the impedance difference
between antenna and chip have been increased. In such as the
RFID tag presented here where all impedances are resistive, the
ratio between impedance difference before and after exposure to
gas molecules is called the differential coefficient of reflectivity, ,
which can
 be calculated as [67]:
(RL −Rr )2 +XL2
= (4)
(RL +Rr )2 +XL2
Where, RL is the resistance part of the load, Rr is the antenna
radiation resistance and XL is the reactive part of the load. The max-
imum  can be obtained if the resistance of the antenna become
optimum after deposition of sensitive film. Such as results from our
previous work on tuning the conductance of the sensitive nanoma-
terial [31], it can be set by adjusting the ratio between the metallic
nanostructures and SWCNTs in the final sensitive film that may be
experienced in the future work. Additionally, by preparing a library
for sensor response toward various analytes, CuO-SWCNT based
H2 S gas sensors can be used in the recent emerging systems such
as IOT for long-term scheme without need to any energy generation
system.
4. Conclusion
In summary, we have fabricated wireless, battery-less gas
sensors by using the conventional RFID tags to detect H2 S at con-
centrations as low as of 100 ppb. The strategy reported to program
the limit of detection of gas sensors by engineering the surface
to volume ratio of flower shaped CuO nanostructures by control-
ling the thermal condition in hydrothermal synthetizing process is
an important advancement in fabrication of highly sensitive gas
sensors. Transferring the released electrons from interaction of
H2 S with CuO nanostructures towards SWCNTs as effective carrier
transfer channel, cause fast response of 7 s in detection of 1 ppm gas
molecules. These results point out the application of fabricated gas
sensors in detection of very low concentration of hazardous H2 S
gas for healthcare and environmental monitoring trends without
using energy generation source.
Acknowledgements
The authors acknowledge Prof. Shams Mohajerzadeh from Uni-
versity of Tehran, School of Electrical and Computer Engineering
for his critical reading of the manuscript and preparing complete
discussion.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2016.03.021.
References
[1] F. Fan, P. Kanjanaboos, M. Saravanapavanantham, E. Beauregard, G. Ingram, E.
Yassitepe, M.M. Adachi, O. Voznyy, A.K. Johnston, G. Walters, G. Kim, Z. Lu,
E.H. Sargent, Colloidal CdSe1-x Sx nanoplatelets with narrow and
continuously-tunable electroluminescence, Nano Lett. (2015).
[2] J.R. Petta, A.C. Johnson, J.M. Taylor, E.A. Laird, A. Yacoby, M.D. Lukin, C.M.
Marcus, M.P. Hanson, A.C. Gossard, Coherent manipulation of coupled electron
spins in semiconductor quantum dots, Science 309 (2005) 2180–2184.
[3] L.S. Zhong, J.S. Hu, H.P. Liang, A.M. Cao, W.G. Song, L.J. Wan, Self-assembled 3D
flowerlike iron oxide nanostructure and their application in water treatment,
Adv. Mater. 18 (2006) 2426–2431.
[4] J. Li, H.Q. Fan, X.H. Jia, Multilayered ZnO nanosheets with 3D porous
architectures: synthesis and gas sensing application, J. Phys. Chem. C 114
(2010) 14684–14691.
[5] W. Yan, H.Q. Fan, Y.C. Zhai, C. Yang, P.R. Ren, L.M. Huang, Low temperature
solution-based synthesis of porous flower-like −Fe2 O3 superstructure and
their excellent gas-sensing properties, Sens. Actuators B 160 (2011)
1372–1379.
[6] Y. Yang, T.X. Liu, Fabrication and characterization of graphene oxide/zinc
oxide nanorods hybrid, Appl. Surf. Sci. 257 (2011) 8950–8954.
[7] G. Zhu, R. Yang, S. Wang, Z.L. Wang, Flexible high-output nanogenerator based
on lateral ZnO nanowire array, Nano Lett. 10 (2010) 3151–3155.
[8] S. Xu, Z. Wang, One-dimensional ZnO nanostructures: solution growth and
functional properties, Nano Res. 4 (2011) 1013–1098.
[9] S. Dilger, C. Lizandara-Pueyo, M. Krumm, S. Polarz, Hierarchical zinc oxide
materials with multiple porosity prepared by ultrafast temperature gradient
chemical gas-phase synthesis, Adv. Mater. 24 (2012) 543–548.
[10] W. Guo, T. Liu, H. Zhang, R. Sun, Y. Chen, W. Zeng, Z. Wang, Gas-sensing
performance enhancement in ZnO nanostructures by hierarchical
morphology, Sens. Actuators B 166–167 (2012) 492–499.
[11] S. Tian, F. Yang, D. Zeng, C. Xie, Solution-processed gas sensors based on ZnO
nanorods array with an exposed (0 0 0 1) facet for enhanced gas-sensing
properties, J. Phys. Chem. C 116 (2012) 10586–10591.
[12] M. D’Arienzo, L. Armelao, C.M. Mari, S. Polizzi, R. Ruffo, R. Scotti, F. Morazzoni,
Macroporous WO3 thin films active in NH3 sensing: role of the hosted Cr
isolated centers and Pt nanoclusters, J. Am. Chem. Soc. 133 (2011) 5296–5304.
[13] S.H. Ko, D. Lee, H.W. Kang, K.H. Nam, J.Y. Yeo, S.J. Hong, C.P. Grigoropoulos, H.J.
Sung, Nanoforest of hydrothermally grown hierarchical ZnO nanowires for a
high efficiency dye-sensitized solar cell, Nano Lett. 11 (2011) 666–671.
[14] N. Bord, G. Crétier, J.-L. Rocca, C. Bailly, J.-P. Souchez, Simultaneous
determination of inorganic anions and organic acids in amine solutions for
sour gas treatment by capillary electrophoresis with indirect UV detection, J.
Chromatogr. A 1100 (2005) 223–229.
[15] J. de Gouw, C. Warneke, T. Karl, G. Eerdekens, C. van der Veen, R. Fall,
Sensitivity and specificity of atmospheric trace gas detection by
proton-transfer-reaction mass spectrometry, Int. J. Mass Spectrom. 223–224
(223) (2003) 365––.
[16] L. Wang, Z. Lou, T. Fei, T. Zhang, Zinc oxide core–shell hollow microspheres
with multi-shelled architecture forgas sensorapplications, J. Mater. Chem. 21
(2011) 19331–19336.
[17] S. Dilger, C. Lizandara-Pueyo, M. Krumm, S. Polarz, Hierarchical zinc oxide
materials with multiple porosity prepared by ultrafast temperature gradient
chemical gas-phase synthesis, Adv. Mater. 24 (2012) 543–548.
[18] W. Guo, T. Liu, H. Zhang, R. Sun, Y. Chen, W. Zeng, Z. Wang, Gas-sensing
performance enhancement in ZnO nanostructures by hierarchical
morphology, Sens. Actuators B 166–167 (2012) 492–499.
[19] M. Abbasi, S.M. Rozati, R. Irani, S. Beke, Synthesis and gas sensing behavior of
nanostructured V2 O5 thin films prepared by spray pyrolysis, Mater. Sci.
Semicond. Process. 29 (2015) 132–138.
[20] T. Zhang, W. Dong, M. Keeter-Brewer, S. Konar, R.N. Njabon, Z.R. Tian, Site
specific nucleation and growth kinetics in hierarchical nanosyntheses of
branched ZnO crystallites, J. Am. Chem. Soc. 128 (2006) 10960–10968.
[21] Y. Zhang, J. Xu, Q. Xiang, H. Li, Q. Pan, P. Xu, Brush-like hierarchical ZnO
nanostructures: synthesis, photoluminescence and gas sensor properties, J.
Phys. Chem. C 113 (2009) 3430–3435.
[22] J. Bae, M.K. Song, Y.J. Park, J.M. Kim, M. Liu, Z.L. Wang, Fiber supercapacitors
made of nanowire-fiber hybrid structures for wearable/flexible energy
storage, Angew. Chem. Int. Ed. 50 (2011) 1683–1687.
[23] A. Sutti, C. Baratto, G. Calestani, C. Dionigi, M. Ferroni, G. Faglia, G.
Sberveglieri, Inverse opal gas sensors: Zn (II)-doped tin dioxide systems for
low temperature detection of pollutant gases, Sens. Actuators B. 130 (2008)
567–573.
[24] L.K. Randeniya, P.J. Martin, A. Bendavid, J. McDonnell, Ammonia sensing
characteristics of carbon-nanotube yarns decorated with nanocrystalline
gold, Carbon 49 (2011) 5265–5270.
[25] C. Xu, J. Wu, U.V. Desai, D. Gao, Multilayer assembly of nanowire arrays for
dye-sensitized solar cells, J. Am. Chem. Soc. 133 (2011) 8122–8125.
[26] G.H. Qiu, S. Dharmarathna, Y.S. Zhang, N. Opembe, H. Huang, S.L. Suib, Facile
microwave-assisted hydrothermal synthesis of CuO nanomaterials and their
catalytic and electrochemical properties, J. Phys. Chem. C 116 (2011) 468–477.
[27] Z.Y. Wang, F.B. Su, S. Madhavi, X.W. Lou, CuO nanostructures supported on Cu
substrate as integrated electrodes for highly reversible lithium storage,
Nanoscale 3 (2011) 1618–1623.
[28] X.Y. Yu, R.X. Xu, C. Gao, T. Luo, Y. Jia, J.H. Liu, X.J. Huang, Novel 3D hierarchical
cotton-candy-like CuO: surfactant-free solvothermal synthesis and
application in As(III) removal, ACS Appl. Mater. Interfaces 4 (2012)
1954–1962.
[29] S. Steinhauer, E. Bruneta, T. Maier, G.C. Mutinati, A. Köck, O. Freudenberg, C.
Gspan, W. Grogger, A. Neuhold, R. Resel, Gas sensing properties of novel CuO
nanowire devices, Sens. Actuators B 187 (2013) 50–57.
[30] A. Bejaoui, J. Guerin, J.A. Zapien, K. Aguir, Theoretical and experimental study
of the response of CuO gas sensor under ozone, Sens. Actuators B Chem. 190
(2014) 8–15.
[31] M. Asad, M.H. Sheikhi, Surface acoustic wave based H2 S gas sensors
incorporating sensitive layers of single wall carbon nanotubes decorated with
Cu nanoparticles, Sens. Actuators B 198 (2014) 134–141.
[32] F. Meng, X. Di, H. Dong, Y. Zhang, C. Zhu, C. Li, Y. Chen, Ppb H2 S gas sensing
characteristics of Cu2 O/CuO sub-microspheres at low-temperature, Sens.
Actuators B 182 (2013) 197–204.
[33] Y. Qin, F. Zhang, Y. Chen, Y. Zhou, J. Li, A. Zhu, Y. Luo, Y. Tian, J. Yang,
Hierarchically porous CuO hollow spheres fabricated via a one-pot
template-free method for high-performance gas sensors, J. Phys. Chem. C 116
(22) (2012) 11994–12000.
 M. Asad, M.H. Sheikhi / Sensors and Actuators B 231 (2016) 474–483
[34] J. Lee, Gas sensors using hierarchical and hollow oxide nanostructures:
Overview, Sens. Actuators B 140 (2009) 319–336.
[35] B. Liu, H.C. Zeng, Mesoscale organization of CuO nanoribbons: formation of
dandelions, J. Am. Chem. Soc. 126 (2004) 8124–8125.
[36] D.P. Volanti, M.O. Orlandi, J. Andres, E. Longo, Efficient microwave-assisted
hydrothermal synthesis of CuO sea urchin-like architectures via a mesoscale
self-assembly, CrystEngComm 12 (2010) 1696–1699.
[37] Y.Y. Xu, D.R. Chen, X.L. Jiao, Fabrication of CuO pricky microspheres with
tunable size by a simple solution route, J. Phys. Chem. B 109 (2005)
13561–13566.
[38] M. Vaseem, A. Umar, S.H. Kim, Y.B. Hahn, Low-temperature synthesis of
flower shaped CuO nanostructures by solution process: formation mechanism
and structural properties, J. Phys. Chem. C 112 (2008) 5729–5735.
[39] M. Asad, M. Fathipour, M.H. Sheikhi, M. Pourfath, High-performance infrared
photo-transistor based on SWCNT decorated with PbS nanoparticles, Sens.
Actuators A 220 (2014) 213–220.
[40] M. Asad, S. Salimian, M.H. Sheikhi, M. Pourfath, Flexible phototransistors
based on graphene nanoribbon decorated with MoS2 nanoparticles, Sens.
Actuators A 232 (2015) 285–291.
[41] R. Byrne, D. Diamond, Chemo/bio-sensor networks, Nat. Mater. 5 (2006)
421–424.
[42] S. De Vito, P. Di Palma, C. Ambrosino, E. Massera, G. Burrasca, M.L. Miglietta, G.
Di Francia, Wireless sensor networks for distributed chemical sensing:
addressing power consumption limits with on-board intelligence, IEEE Sens. J.
11 (2011) 947–955.
[43] R.A. Potyrailo, N. Nagraj, C. Surman, H. Boudries, H. Lai, J.M. Slocik, et al.,
Wireless sensors and sensor networks for homeland security applications,
TrAC Trends Anal. Chem. 40 (2012) 133–145.
[44] R.A. Potyrailo, C. Surman, N. Nagraj, A. Burns, Materials and transducers
toward selective wireless gas sensing, Chem. Rev. 111 (2011) 7315–7354.
[45] L. Ruiz-Garcia, L. Lunadei, P. Barreiro, J.I. Robla, A review of wireless sensor
technologies and applications in agriculture and food industry: state of the art
and current trends, Sensors 9 (2009) 4728–4750.
[46] J.F. van Staden, R.I. Stefan-van Staden, S.C. Balasoiu, Wireless electrochemical
sensors: a tool for process control past, present and the future, Crit. Rev. Anal.
Chem. 40 (2010) 226–233.
[47] M. Asad, M.H. Sheikhi, M. Pourfath, M. Moradi, High sensitive and selective
flexible H2 S gas sensors based on Cu nanoparticle decorated SWCNTs, Sens.
Actuators B 210 (2015) 1–8.
[48] L. Soleymani, Z. Fang, E.H. Sargent, S.O. Kelley, Programming the detection
limits of biosensors through controlled nanostructuring, Nat. Nanotechnol. 4
(2009) 844–848.
[49] B. Liu, H.C. Zeng, Hydrothermal synthesis of ZnO nanorods in the diameter
regime of 50 nm, J. Am. Chem. Soc. 125 (2003) 4430–4431.
[50] H. Zhang, X. Zhang, H. Li, Z. Qu, S. Fan, M. Ji, Hierarchical growth of Cu2 O
doubletower-tip-like nanostructures in water/oil microemulsion, Cryst.
Growth Des. 7 (2007) 820–824.
[51] S. Guha, D. Peebles, T.J. Wieting, Zone-center (q = 0) optical phonons in CuO
studied by Raman and infrared spectroscopy, Phys. Rev. B 43 (1991) 13092.
[52] G. Kliche, Z.V. Popovic, Far-infrared spectroscopic investigations on CuO, Phys.
Rev. B 42 (1990) 10060.
[53] Z.V. Popovic, C. Thomsen, M. Cardona, R. Liu, G. Stanisic, R. Kremer, W. Konig,
Phonon characterization of Bi2 (Sr1-x Cax )2 CuO6+( by infrared and Raman
spectroscopy, Solid State Commun. 66 (1988) 965–969.
[54] L. Degiorgi, E. Kaldis, P. Wachter, Electronic and phononic structure of
La1-x Srx CuO4 , Physica C 153–155 (1988) 657–658.
483
[55] S.N. Narang, V.B. Kartha, N.D. Patel, Fourier transform infrared spectra and
normal vibrations of CuO, Physica C 204 (1992) 8–14.
[56] J.P. Liu, X.T. Huang, Y.Y. Li, K.M. Sulieman, X. He, F.L. Sun, Hierarchical
nanostructures of cupric oxide on a copper substrate: controllable
morphology and wettability, J. Mater. Chem. 16 (2006) 4427–4434.
[57] G.F. Zou, H. Li, D.W. Zhang, K. Xiong, C. Dong, Y.T. Qian, Well-aligned arrays of
CuO nanoplatelets, J. Phys. Chem. B 110 (2006) 1632–1637.
[58] M.S. Dresselhaus, G. Dresselhaus, A. Jorio, A.G.S. Filho, R. Saito, Raman
spectroscopy on isolated single wall carbon nanotubes, Carbon 40 (2002)
2043–2061.
[59] T. Yu, X. Zhao, Z.X. Shen, Y.H. Wu, W.H. Su, Investigation of individual CuO
nanorods by polarized micro-Raman scattering, J. Cryst. Growth 268 (2004)
590–595.
[60] D. Chen, G. Shen, K. Tang, Y. Qian, Large-scale synthesis of CuO shuttle-like
crystals via a convenient hydrothermal decomposition route, J. Cryst. Growth
254 (2003) 225–228.
[61] N.S. Ramgir, S.K. Ganpathi, M. Kaur, N. Datta, K.P. Muthe, D.K. Aswal, S.K.
Gupta, J.V. Yakhmi, sub-ppm H2 S sensing at room temperature using CuO thin
films, Sens. Actuators B 151 (2010) 90–96.
[62] J. Bardeen, W.H. Brattain, W. Shockley, Investigation of Oxidation of Copper
by Use of Radioactive Cu Tracer, J. Chem. Phys. 14 (1946) 714.
[63] J. Chen, K. Wang, L. Hartman, W. Zhou, H2 S detection by vertically aligned
CuO nanowire array sensors, J. Phys. Chem. C 112 (2008) 16017–16021.
[64] N.S. Ramgir, C.P. Goyal, P.K. Sharma, U.K. Goutam, S. Bhattacharya, N. Datta,
M. Kaur, A.K. Debnath, D.K. Aswal, S.K. Gupta, Selective H2 S sensing
characteristics of CuO modified WO3 thin films, Sens. Actuator B 188 (2013)
525–532.
[65] M. Kaur, N. Jain, K. Sharma, S. Bhattacharya, M. Roy, A.K. Tyagi, S.K. Gupta, J.V.
Yakhmi, Room-temperature H2 S gas sensing at ppb level by single crystal
In2 O3 whiskers, Sens. Actuators B 133 (2008) 456–461.
[66] S. Mubeen, T. Zhang, N. Chartuprayoon, Y. Rheem, A. Mulchandani, N.V.
Myung, M.A. Deshusses, Sensitive Detection of H2 S Using Gold Nanoparticle
Decorated Single-Walled Carbon Nanotubes, Anal. Chem. 82 (2010) 250–257.
[67] F. Terman, Radio Engineering’s Handbook, McGraw-Hill, New York, 1943.
Biographies
Mohsen Asad worked as a research engineer at Semiconductor Device Research
Center, School of Electrical and Computer Engineering, Shiraz University, Iran. He
has worked several years in the fields of MEMS/NEMS devices and chemical sensors.
He is currently working at School of Electrical and Computer Engineering, University
of Waterloo on design and fabrication of wearable and flexible electronics to monitor
the vital signs of human and also environmental pollutants.
Mohammad Hossein Sheikhi received his BSc (1994) degree in electrical engineer-
ing from Shiraz University, Shiraz, Iran, the MSc (1996) degree from Sharif University
of Technology, Tehran, Iran and the PhD degree in electrical engineering from Tar-
biat Modarres University, Tehran in 2000. He was selected as the distinguished PhD
student graduated from Tarbiat Modarres University in 2000. He joined Tohokou
University, Sendai, Japan, as a Research Scientist in 2000. After joining Shiraz Univer-
sity in 2001, he focused on the optoelectronics, nanosensors, and nanotransistors. He
is currently the Associate Professor and founder of Semiconductor Device Research
Center, Shiraz University, Shiraz, Iran.