Journal of Alloys and Compounds 618 (2015) 455–462

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Gas sensing properties of zinc stannate (Zn2SnO4) nanowires prepared

by carbon assisted thermal evaporation process
T. Tharsika a, A.S.M.A. Haseeb a,⇑, S.A. Akbar b, M.F.M. Sabri a, Y.H. Wong a
a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Center for Industrial Sensors and Measurements (CISM), Department of Materials Science and Engineering, Ohio State University, 2041 College Road, Columbus, OH 43210, USA

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

Article history: Zn2SnO4 nanowires are successfully synthesized by a carbon assisted thermal evaporation process with
Received 23 June 2014 the help of a gold catalyst under ambient pressure. The as-synthesized nanowires are characterized by X-
Received in revised form 18 August 2014 ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron
Accepted 22 August 2014
microscopy (TEM) equipped with an energy dispersive X-ray spectroscopy (EDS). The XRD patterns
Available online 2 September 2014
and elemental mapping via TEM–EDS clearly indicate that the nanowires are Zn2SnO4 with face centered
spinel structure. HRTEM image confirms that Zn2SnO4 nanowires are single crystalline with an interpla-
Keywords:
nar spacing of 0.26 nm, which is ascribed to the d-spacing of (3 1 1) planes of Zn2SnO4. The optimum pro-
Zinc stannate
Nanowires
cessing condition and a possible formation mechanism of these Zn2SnO4 nanowires are discussed.
Carbon assisted thermal evaporation Additionally, sensor performance of Zn2SnO4 nanowires based sensor is studied for various test gases
Gas sensors such as ethanol, methane and hydrogen. The results reveal that Zn2SnO4 nanowires exhibit excellent
Ethanol sensitivity and selectivity toward ethanol with quick response and recovery times. The response of the
Zn2SnO4 nanowires based sensors to 50 ppm ethanol at an optimum operating temperature of 500 °C
is about 21.6 with response and recovery times of about 116 s and 182 s, respectively.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction
Metal oxide nanostructures with well-defined morphologies
have attracted a great deal of attention because of their shape, size
and surface dependent properties [1,2]. The ability to control the
size and shape of nanostructures is crucial as it affects their overall
properties. One dimensional nanostructures, for example, are of
immense interest in the field of nanotechnology. To date, intensive
studies have been carried out on binary metal oxides nanostruc-
tures in several applications [3,4]. There is a continuing need for
specially designed semiconductors that has led to an interest in
ternary oxides, such as Zn2TiO4 [5], CdSnO3 [6], ZnSnO3 [7], LiNbO3
[8], Cd2SnO4 [9], Zn2SnO4 [10–12], BaTiO3 [13], CdIn2O4 [14], CuFe-
O2 [15], SrTiO3 [13], and Cd2GeO4 [16]. Ternary oxides provide
greater flexibility to tune the chemical and physical properties of
the materials by varying the compositions [17].
Among these ternary oxides, Zn2SnO4 is an important n-type
semiconductor with a large band gap of 3.6 eV [18], which is often
⇑ Corresponding author. Tel.: +60 3 7967 4492; fax: +60 3 7967 5317.
E-mail addresses: tharsika@siswa.um.edu.my (T. Tharsika), haseeb@um.edu.my
(A.S.M.A. Haseeb), akbar.1@osu.edu (S.A. Akbar), faizul@um.edu.my (M.F.M. Sabri),
yhwong@um.edu.my (Y.H. Wong).
called zinc tin oxide (ZTO). Studies verified that bulk Zn2SnO4 has
high electron mobility and conductivity, good thermal stability,
chemical sensitivity, and low visible light absorption [19]. For
instance, Zn2SnO4 nanowires have been successfully used as elec-
trodes in lithium ion batteries for its stability [20]. Hierarchical
macroporous Zn2SnO4 nanoparticles also have highly efficient per-
formance in dye-sensitized solar cells due to its superior light scat-
tering ability [21]. Zigzag Zn2SnO4 nanowires have also been
shown to exhibit high sensor performance in detecting toxic and
volatile organic compounds with sensitivity towards 50 ppm etha-
nol around 12 [17]. Chen et al. [22] reported flower-like hierarchi-
cal Zn2SnO4 nanostructures based sensors that exhibited enhanced
ethanol sensitivity of 8 when exposed at 20 ppm, which is ascribed
to high specific surface area and increased number of surface
defects. Further, hollow Zn2SnO4 microcrystals showed high sensi-
tivity towards H2S due to large surface area [23]. Recently, Park
et al. [24] demonstrated that Zn2SnO4-core/ZnO-shell nanorod
based sensors showed enhanced response to NO2 with a sensitivity
of 173–498% at a concentration range of 1–5 ppm. This value was
2–5 folds higher than that of the pristine Zn2SnO4 nanorod sensor
owing to encapsulation of Zn2SnO4-core by ZnO-shell, and forma-
tion of heterojunction which acted as a lever in electron transfer.
However, along with high sensitivity, there is a need to design a
selective of sensor.

http://dx.doi.org/10.1016/j.jallcom.2014.08.192
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
456 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462
Several efforts have been made to synthesize Zn2SnO4 nano-
structures using various processing routes such as thermal evapo-
ration [19,25–27], hydrothermal method [28,29], catalyst-free
vapour-solid process [17], solvothermal method [10,12,30], carbo-
thermal reduction [20], and chemical vapour deposition [31].
Among these approaches, the carbon assisted thermal evaporation
process is a simple and convenient way to grow large amount of
Zn2SnO4 nanowires under ambient pressure. In the synthesis pro-
cess, ZnO and SnO2 metal oxides are simultaneously evaporated
with the help of activated carbon powder. The activated carbon
enhances the reaction rate by performing as reducing agent and
creates the Zn and Sn vapours in an ambient pressure [32]. Then
the vapours are transferred to the substrate which is at a lower
temperature than the vapour source located at the center of the
furnace, and reacts on the Au catalyst. Zn2SnO4 ternary oxide nano-
wires are formed based on the vapour–liquid–solid (VLS) growth
mechanism [33,34]. Structural properties and optimum condition
for the growth of Zn2SnO4 nanowires are studied by varying
growth time, deposition position of the substrate and furnace tem-
perature. Zn2SnO4 nanowires based sensors are configured as high
performance resistor-type sensors and are used to investigate the
performance of several test gases including ethanol, hydrogen
and methane. Specifically, selective ethanol sensors are designed
that show promising potential.
2. Experimental procedure
2.1. Synthesis of Zn2SnO4 nanowires
Zn2SnO4 nanowires were synthesized via carbon assisted thermal evaporation
process under ambient pressure [35]. A schematic of the experimental setup is
shown in Fig. 1(a). Commercial ZnO, SnO2 and activated carbon powders were used
as source materials. Gold interdigitated alumina was used as the substrate and
99.99% purified Ar was used as a carrier gas to transfer Zn and Sn vapour from
the source to the substrate. A mixture of ZnO, SnO2, and activated carbon powder
with the molar ratio of 9:1:10 was prepared. Prior to loading the mixture inside
the furnace, the powder mixture was placed in a 4.5 cm diameter jar with zirconia
balls to perform planetary ball milling (Retsch PM 400). The milling was carried out
for 8 h to get a homogeneous mixture of particles with an average size of 150 nm. A
thin gold layer of around 40 Å thickness was applied to an alumina substrate by
sputtering from a gold target at a rate of about 1.25 Å/s for 30 s using SPI module
sputter coater. This Au layer is used as a catalyst to grow the Zn2SnO4 nanowires.
The milled powder mixture was transferred into a quartz boat and then it was
placed in the center of a horizontal tube furnace (Lindberg Blue M). Then the alu-
mina substrate was placed in various position from 3 cm to 12 cm away from the
source powder at a step of 3 cm. Prior to exposure to Ar gas with a constant flow
rate, the furnace was purged for 15 min to remove unwanted contamination inside
the quartz tube. Then Ar was introduced with a constant flow rate of 25 sccm
throughout the process. Subsequently, the temperature of the furnace was
increased from room temperature to various furnace temperatures (800 °C,
850 °C, 900 °C and 950 °C) at a rate of 30 °C/min and maintained for various growth
times (15, 30, 60, 90 and 120 min). Finally, the furnace was cooled down to room
temperature. A light gray layer was observed on the alumina substrate. The temper-
ature variation as a function of distance from the center of the furnace was mea-
Fig. 1. (a) Experimental setup for the growth of Zn2SnO4 nanowires and (b) temperature profile as a function of distance from the center of the furnace at 25 sccm Ar flow.
sured which is presented in Fig. 1(b). This temperature profile helps to determine
the optimum location of the substrate and growth temperature for the formation
of nanowires.
2.2. Characterization
The morphology, structural and elemental distribution of the nanowires were
characterized by X-ray diffraction (XRD: Siemens D-5000), field-emission scanning
electron microscopy (FESEM: Auriga Zeiss Ultra-60) equipped with an energy dis-
persive X-ray spectroscopy, and high resolution transmission electron microscopy
(HRTEM: FEI Tecnai F-20 microscopy). Selected area electron diffraction (SAED) pat-
tern was also obtained. TEM samples were prepared by sonication of the nanowires
extracted from the substrate in deionized water. The nanowire suspension was then
drop coated on a carbon-coated copper grid (300 mesh).
2.3. Gas sensing measurements
Zn2SnO4 nanowires grown on Au printed interdigitated electrode having a
dimension of 5 mm  5 mm was used as a gas sensor. Gold wire with a diameter
of 0.2 mm was connected to Au electrode using Au paste followed by curing at
700 °C for 2 h. The sensor was then placed inside a horizontal tube furnace and
sensing measurements were carried out in the presence of various test gases. The
sensitivity of the sensor is defined as (Ra  Rg)/Ra, where Ra and Rg are the resis-
tances measured in nitrogen and tested gas, respectively. The response and recov-
ery times are determined as the time taken by the sensor to attain 90% of the total
resistance change for response and recovery, respectively [36].
3. Results and discussion
3.1. Morphology and structural analysis of Zn2SnO4 nanowires
Fig. 2 shows the XRD patterns of Zn2SnO4 nanowires obtained
for samples prepared by carbon assisted thermal evaporation pro-
cess at 900 °C for a growth time of 120 min. Ternary compound of
face centered cubic spinel Zn2SnO4 phase is detected in the XRD
patterns which is denoted as ZTO in Fig. 2. These peaks are consis-
tent with the JCPDS card no of 24-1470. Au (1 1 1) and alumina
peaks are noticed which originate from the gold coated alumina
substrate. A small quantity of ZnO phase is also identified. The
presence of sharp and strong X-ray diffraction peaks suggests that
the Zn2SnO4 nanowires have good crystallinity.
We carried out experiments to find the effect of growth times,
growth temperature, and substrate position from the center of
the furnace on the growth of Zn2SnO4 nanowires. Fig. 3 shows the
FESEM micrographs of nanostructures grown at different furnace
temperatures with various deposition positions, and the growth
temperatures of nanostructures at various deposition positions
are illustrated in Table 1. At low furnace temperature of 800 °C,
no nanowires are observed with different deposition positions
(Fig. 3(a)–(d)). The range of growth temperatures between 633 °C
and 802 °C are not high enough to produce sufficient Zn and Sn
vapour pressure to grow the nanowires (see Table 1) and Au thin
film cannot break up into nanosized droplets [37]. Therefore no
 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462 457

observed at the deposition position of 9 cm in Fig 3(k). The length

Fig. 2. XRD patterns of Zn2SnO4 nanowires.
nanowires are observed. At furnace temperature of 850 °C, nano-
wires initiate to grow at the substrate position of 6 cm except other
places (Fig. 3(e)–(h)). Lengths of nanowires are very short and
thicker in diameter. Therefore, the growth temperature of nano-
wires is found to be around 833 °C (Table 1). At moderate furnace
temperature of 900 °C, more heavily populated nanowires are
of nanowires is increased to several tens of micrometres with thin-
ner diameter compared to furnace temperature of 850 °C. The
growth temperature of nanowires is observed at 834 °C (Table 1),
which is consistent with the furnace temperature of 850 °C at the
deposition position of 6 cm. At high furnace temperature of
950 °C, a fewer nanowires are observed anywhere on the substrate
(Fig. 3(m)–(p)). This happens because the growth temperatures for
various deposition positions are too high for the condensation of
metal vapours. Thus no nanowires are observed.
From these results, we can conclude that the optimum growth
temperature for nanowire growth is around 834 °C at the deposi-
tion position of 9 cm with furnace temperature of 900 °C. Furnace
temperatures of 800 °C and 850 °C are not high enough to produce
sufficient vapour pressure to grow the nanowires. On the other
hand, the furnace temperature of 950 °C is too high for the conden-
sation of the metal vapours.
Fig. 4(a)–(e) exhibits FESEM micrographs for Zn2SnO4 nanowires
grown on Au/alumina substrate at different growth times. The
insets of figures show the single Zn2SnO4 nanowire corresponding
to the growth time. Growth time was varied from 15 min to
120 min, while the center position temperature of the tube furnace

Fig. 3. FESEM images of the nanostructures fabricated at different furnace temperatures with various deposition positions of substrate from the center of the furnace.

Table 1
Growth temperatures of nanostructures obtained at different furnace temperatures and various substrate positions.

Substrate position from center of furnace (cm) Growth temperatures for different furnace temperatures (°C)
800 850 900 950
3 802 854 900 956
6 780 833 880 935
9 737 788 834 893
12 633 684 730 796
458 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462
Fig. 4. FESEM micrographs of the nanostructures synthesized at different growth times on Au/alumina substrate at 900 °C: (a) 15 min, (b) 30 min, (c) 60 min, (d), 90 min and
(e) 120 min.
was kept at of 900 °C. As can be seen in Fig. 4(a)–(c), Zn2SnO4 nano-
wires grow sparsely on Au/Alumina substrate with 2–6 lm in
length. But, Fig. 4(d) and (e) exhibits that the Zn2SnO4 nanowires
grow homogeneously on the entire Au/Alumina substrate. The
length of the nanowires increases from 2 to 50 lm with increasing
growth time from 15 min to 120 min. On the other hand, diameter
of the nanowire was observed as decreasing tendency with increas-
ing growth time, which were measured around 80 nm, 72 nm,
68 nm, 63 nm and 58 nm for the growth time of 15 min, 30 min,
60 min, 90 min and 120 min, respectively. The decrease in diameter
of nanowire may be attributed to the re-evaporation of materials
during longer growth time. The smaller nanowire diameter can be
explained by the Gibbs–Thomson effect [38]. An increasing reaction
time and thereby decreasing supersaturating vapour lead to the
diameter of the nanowire become smaller [37]. From this analysis,
we can conclude that the concentration and length of Zn2SnO4
nanowires increased and diameter of nanowire decreased with
increasing growth time.
FESEM image in Fig. 5(a) shows that large quantity of one-
dimensional Zn2SnO4 nanowires are obtained with an average
length of 10 lm and diameter ranging from 20 to 80 nm. It is seen
that the nanowire has a distinct tip as clearly shown in the inset of
Fig. 5(b). EDAX spectrum of the tip was taken and is shown in
Fig. 5(b). It reveals that point scan of the tip confirms the presence
of Au, Zn, Sn and O. It is believed that while Zn, Sn and O come from
lower layers of Zn2SnO4 nanowires, Au is at the tip of the nanowire
that acts as a catalyst for the growth of Zn2SnO4 nanowire via the
vapour–liquid–solid mechanism [39].
Fig. 6 presents a representative scanning-mode TEM (STEM)
image of the nanowire and the corresponding Zn, O and Sn elemen-
tal maps. As shown in Fig. 6(c)–(e), all elements in the Zn2SnO4
nanowire are homogeneously distributed over the entire surface
of the nanowire. From the distribution of elements, we can con-
clude that all nanowires are composed of Zn2SnO4. These observa-
tions are consistent with Zn2SnO4 nanowires obtained via catalyst
free growth method by Liang et al. [26].
A representative low magnification TEM image of Zn2SnO4
nanowire having an average diameter of 25 nm is depicted in
Fig. 7(a). As we can see in Fig. 7(b), the nanowire shows the gold
cap at its tip indicating that the growth of nanowire is via the
well-known vapour–liquid–solid (VLS) mechanism. The clear lat-
tice fringes in Fig. 7(c) of the HRTEM image show the single
crystalline nature of the nanowire with an interplanar spacing of
0.26 nm, which is ascribed to the d-spacing of (311) planes of
Zn2SnO4 [18,20]. Thus the nanowire growth direction is believed
to be [3 1 1] [40]. The SAED pattern also demonstrates that the
nanowire is a single crystal (Fig. 7(d)).
We propose a growth mechanism for the synthesized Zn2SnO4
nanowires from the aforementioned experimental results, which
is depicted in Fig. 8. It is believed that the growth is governed by
the following chemical reactions.
ZnOðsÞ þ SnO2ðsÞ þ CðsÞ ! Znðv Þ þ Snðv Þ þ COðv Þ =CO2ðv Þ ð1Þ
2Znðv Þ þ Snðv Þ þ 4COðv Þ ! Zn2 SnO4ðsÞ þ 4CðsÞ ð2Þ
 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462 459

Fig. 5. (a) Typical low magnification FESEM image of Zn2SnO4 nanowires and (b) EDAX spectrum of tip of the nanowires.

Fig. 6. STEM–EDS analysis of nanowire: (a) STEM image of Zn2SnO4 nanowire, (b) enlarged image of the map area in (a), and corresponding mapping elements of Zn (c), O (d),
and Sn (e).

Fig. 7. (a) Low magnification TEM images of a single Zn2SnO4 nanowire deposited at 120 min; (b) nanowire with a catalyst at its tip; (c) HRTEM image and corresponding (d)
SAED pattern of Zn2SnO4 nanowire.
460 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462
Fig. 8. Schematic representation of Zn2SnO4 nanowires grown on Au/alumina substrate.
In this experiment, Zn and Sn are vaporized after reduction by
activated carbon in the higher-temperature region (900 °C), which
is the center of the furnace temperature. Then the vapours are
transported to the substrate which is located downstream at a
lower temperature region (830 °C). The vapour is composed of
Zn and Sn that reacts with the gold nanoparticle on the substrate
and form Au–Sn–Zn liquid alloy droplet [41]. This alloy further
reacts with oxygen and nucleates Zn2SnO4 nanowire. Although
our experiments were done in purified Ar (99.99%) atmosphere,
the oxygen could come from the small amount of oxygen in Ar
(10 s of ppm). When more Zn and Sn vapour are dissolved in the
liquid droplet, Zn2SnO4 would reach the supersaturated state. Sub-
sequently, saturated solid Zn2SnO4 precipitates from the droplets
in the form of Zn2SnO4 nanowires by absorbing more Zn and Sn
vapour. So, Zn2SnO4 nanowires continue to grow with gold at the
tip. On the other hand, carbon soot was observed on the wall of
the quartz tube at 18 cm from the center of the furnace. Therefore,
the carbon soot has from CO according to reaction (2). It is believed
that re-oxidation was performed between Zn–Sn vapours and CO.
Therefore, carbon soot was detected on the interior wall of quartz
tube.
ZnO nanowires coexist with Zn2SnO4 nanowires in our product
which is presented in XRD analysis. In this present process, more
ZnO is used as compared to SnO2 (molar ratio between ZnO and
SnO2 is 9:1). It is believed that, ZnO nanowires formed due to dif-
ferent speeds of vaporization of ZnO and SnO2, and excess ZnO
[39]. The control of the evaporation of source mixture is crucial
for the synthesis of ternary oxide Zn2SnO4 nanowires. Single phase
Zn2SnO4 ternary oxide nanowires might be acquired under opti-
mum conditions. Jie et al. [39] reported that the ratio between ter-
nary and binary oxide nanowires in the end product is dependent
on the growth temperature, substrate position temperature and
the ratio of source mixture.
3.2. Gas sensing properties of Zn2SnO4 nanowires
The gas sensing tests were conducted for various gases to exam-
ine the sensor performance of the Zn2SnO4 nanowire. The sensitiv-
ity of a gas sensor is usually dependent on an optimum
temperature [42]. The sensitivity of the sensor to 20 ppm of etha-
nol, hydrogen and methane were tested to determine an optimum
temperature, which are shown in Fig. 9(a). It can be observed that
the sensitivity of the sensor varied with the operating temperature.
From the results of ethanol, we can see that the sensitivity
increases with temperature up to 500 °C and then decreases. Thus,
500 °C is determined to be the optimum temperature for ethanol
detection. Similar trend is also obtained for hydrogen and methane
with much less sensitivity compared to ethanol, shown in Fig. 9(a).
Very similar values of optimum operating temperature are
observed for all gases, though literature indicates varying optimum
temperatures for different gases [43]. The variations in the opti-
mum operating temperature for different gases suggest variation
in the adsorption and desorption characteristics of the gases. This
property is utilized to design selective sensors. However, all sen-
sors are operated over a wide range of temperature (300–550 °C)
leading to different thermal energies for the surface reactions
[44]. The sensitivity is very low below the operating temperature
of 300 °C. It may be attributed to the adsorbed gas molecules not
being sufficiently activated to react with the adsorbed oxygen
ion species on the surface of the sensing medium [44]. As the tem-
perature is further increased above 300 °C, the activation energy
barrier is surmounted allowing gas molecules react with surface
adsorbed oxygen leading to the change in resistance and hence
enhanced sensitivity [45]. The sensitivity of the sensor is observed
to decrease above the temperature of 500 °C. This is a commonly
observed phenomenon in resistive sensors since at higher temper-
atures desorption becomes dominant that leads to the decrease in
sensitivity [45,46].
Representative dynamic gas responses of the Zn2SnO4 sensor is
measured upon exposure to ethanol, hydrogen and methane at
500 °C and the results are shown in Fig. 9(b)–(d). These results
imply that the sensor exhibits a strong response for ethanol and
very little response for other two gases at 500 °C. One of the key
performance indicators for a gas sensor is to have good selectivity.
Zn2SnO4 nanowire sensor exhibits high selectivity toward ethanol
compared to the other two gases. The response increases rapidly
with increasing concentration of ethanol from 20 ppm to
400 ppm. This response curve reveals that the sensor could detect
ethanol in a wide range. Five cycles were recorded with the con-
centrations of 20, 50, 100, 250 and 400 ppm. Sensitivities of etha-
nol corresponding to the above concentrations are 4.9, 21.6, 60.8,
254, and 468, respectively. The sensitivities of hydrogen and meth-
ane to 400 ppm are 4.75 and 2.7, respectively, which is around 100
times lower than those for ethanol. The response and recovery
times for ethanol are 120 s and 200 s, respectively for the concen-
tration of 20 ppm. Response and recovery times are decreased from
120 s to 100 s and 200 s to 60 s, respectively, with increasing con-
centration from 20 ppm to 400 ppm. The observed high sensitivity
and selectivity of Zn2SnO4 nanowires demonstrate that this mate-
rial is a suitable candidate for monitoring ethanol.
3.3. Gas sensing mechanism of Zn2SnO4 nanowires
Gas adsorption and desorption is a common mechanism for gas
sensing [47]. Metal oxide based sensor is exposed to air, which
results in O2 adsorption on the surface of the material. Oxygen
 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462
Fig. 9. (a) Sensitivity of Zn2SnO4 nanowire sensor as a function of the operating temperature for various gases with the concentration of 50 ppm; dynamic response for (b)
ethanol, (c) hydrogen, and (d) methane gas, respectively.
molecules trap electrons from the conduction band of the material
because of strong electronegativity of the oxygen atom and hence
induces oxygen adsorption [48]. The stable O 2 ions are dominant
when the temperature is below 100 °C. At moderate temperature
between 100 and 300 °C, O ion species is more abundant than
2
O2 and O ion is stable above 300 °C [49–51]. Due to oxygen
adsorption, electron concentration in the conduction band drops,
and the resistance of the material rises for an n-type oxide. When
a reducing gas is introduced, a chemical reaction takes place
between the reducing gas and the surface adsorbed oxygen, which
results in electron injection to the surface of the material that
results in the decrease of the resistance of the material.
A similar mechanism is at play in our Zn2SnO4 based sensor.
Optimum sensing was performed above 300 °C for all test gases.
Therefore O2 ion species interact with test gases. When hydrogen
is introduced, it reacts with the chemisorbed oxygen and produces
H2O, which is expressed in Eq. (3) [50].
H2 þ O2
ðadsÞ ! H2 OðgÞ þ 2e

Kohl [52] reported the methane dissociation mechanism. They
stated that methane dissociates to a methyl group and hydrogen.
Subsequently, combination of adsorbed hydrogen atoms produces
hydrogen molecule which is described by Eqs. (4) and (5). Then the
hydrogen molecule reacts with the adsorbed oxygen on the Zn2-
SnO4 surface and creates H2O, which is shown by Eq. (6).
CH4 $ CH3ðadsÞ þ HðadsÞ
HðadsÞ þ HðadsÞ $ H2
H2 þ O2
ðadsÞ ! H2 OðgÞ þ 2e 
Catalytic oxidation of ethanol gas is known to occur through
two different routes depending on the acid or base properties of
the catalyst surface. One is a dehydrogenation route through
CH3CHO intermediate (on the basic surface) and a dehydration
461
route through a C2H4 intermediate (on the acidic surface) [53].
But, Zn2SnO4 is an n-type semiconductor. Thus it acts as basic
oxide. Therefore dehydrogenation is favoured, providing CH3CHO
as the main intermediate when C2H5OH is introduced. Then it
undergoes consequent oxidation to form CO2 and H2O which is
shown in Eqs. (7) and (8) [53].
C2 H5 OH ! CH3 CHOðadsÞ þ H2ðgÞ ð7Þ
CH3 OHðadsÞ þ 5O2
ðadsÞ ! 2CO2ðgÞ þ 2H2 OðgÞ þ 10e

ð8Þ
When the gas sensor is exposed to the test gas, the resistance of
the material decreases and the sensitivity increases due to the
injection of electrons to the oxide as a result of the above reactions.
According to these three test gas equations, the electron donating
effect of ethanol is stronger than that of the hydrogen and methane
gases. Hence, the sensitivity of ethanol is greater than that of the
other gases for the same concentration.
ð3Þ
4. Conclusions
We report the optimum growth condition of Zn2SnO4 nano-
wires through the carbon assisted thermal evaporation process
and its gas sensing properties. A suggested growth mechanism of
Zn2SnO4 nanowires is discussed. The obtained Zn2SnO4 nanowires
exhibit excellent gas sensing properties to ethanol, in terms of high
response, fast response and recovery times, as well as good selec-
ð4Þ tivity. The results show that Zn2SnO4 nanowires-based sensor is
a potential candidate for high performance ethanol gas sensing.
ð5Þ
Acknowledgments
ð6Þ
The authors acknowledge financial support of High Impact
Research grant (UM.C/HIR/MOHE/ENG/26, Grant No. D000026-
16001) and UMRG grant (UMRG No: RP021-2012D) from Univer-
sity of Malaya. Ms. T. Tharsika acknowledges the Bright Spark Unit,
University of Malaya for a Bright Spark scholarship.
462 T. Tharsika et al. / Journal of Alloys and Compounds 618 (2015) 455–462

References [27] Y. Du, P. Ding, Thermal evaporation route to zinc stannate nanowires and the
cathodoluminescence of the individual nanowires, J. Alloys Comp. 502 (2010)
L14–L16.
[1] J. Wang, D.N. Tafen, J.P. Lewis, Z. Hong, A. Manivannan, M. Zhi, M. Li, N. Wu,
[28] A. Annamalai, Y.D. Eo, C. Im, M.-J. Lee, Surface properties and dye loading
Origin of photocatalytic activity of nitrogen-doped TiO2 nanobelts, J. Am.
behavior of Zn2SnO4 nanoparticles hydrothermally synthesized using different
Chem. Soc. 131 (2009) 12290–12297.
mineralizers, Mater. Charact. 62 (2011) 1007–1015.
[2] F. Zuo, L. Wang, T. Wu, Z. Zhang, D. Borchardt, P. Feng, Self-doped Ti3+
[29] M. Mary Jaculine, C. Justin Raj, S. Jerome Das, Hydrothermal synthesis of highly
enhanced photocatalyst for hydrogen production under visible light, J. Am.
crystalline Zn2SnO4 nanoflowers and their optical properties, J. Alloys Comp.
Chem. Soc. 132 (2010) 11856–11857.
577 (2013) 131–137.
[3] S. Sen, P. Kanitkar, A. Sharma, K.P. Muthe, A. Rath, S.K. Deshpande, M. Kaur, R.C.
[30] G. Sun, S. Zhang, Y. Li, Solvothermal synthesis of Zn2SnO4 nanocrystals and
Aiyer, S.K. Gupta, J.V. Yakhmi, Growth of SnO2/W18O49 nanowire hierarchical
their photocatalytic properties, Int. J. Photoenergy 2014 (2014) 1–4.
heterostructure and their application as chemical sensor, Sens. Actuators, B
[31] J. Chen, L. Lu, W. Wang, Zn2SnO4 nanowires as photoanode for dye-sensitized
147 (2010) 453–460.
solar cells and the improvement on open-circuit voltage, J. Phys. Chem. C 116
[4] J. Dai, C. Xu, J. Guo, X. Xu, G. Zhu, Y. Lin, Brush-like SnO2/ZnO hierarchical
(2012) 10841–10847.
nanostructure: synthesis, characterization and application in UV
[32] O. Fouad, G. Glaspell, M. El-Shall, Growth and characterization of ZnO, SnO2
photoresponse, Aip Adv. 3 (2013) 062108.
and ZnO/SnO2 nanostructures from the vapor phase, Top. Catal. 47 (2008) 84–
[5] Y. Yang, R. Scholz, H.J. Fan, D. Hesse, U. Gosele, M. Zacharias, Multitwinned
96.
spinel nanowires by assembly of nanobricks via oriented attachment: a case
[33] A.M. Morales, C.M. Lieber, A laser ablation method for the synthesis of
study of Zn2TiO4, ACS Nano 3 (2009) 555–562.
crystalline semiconductor nanowires, Science 279 (1998) 208–211.
[6] K. Tang, L. Wang, A facile synthesis of highly porous CdSnO3 nanoparticles and
[34] Q. Hu, P. Jiang, H. Xu, Y. Zhang, S. Wang, X. Jia, W. Tang, Synthesis and
enhanced lithium-ion battery performance, J. Mater. Chem. A (2014) 4970–
photoluminescence of Zn2SnO4 nanowires, J. Alloys Comp. 484 (2009) 25–27.
4974.
[35] T. Tharsika, A.S.M.A. Haseeb, S.A. Akbar, M.F.M. Sabri, Co-synthesis of ZnO/
[7] J.M. Wu, C.-Y. Chen, Y. Zhang, K.-H. Chen, Y. Yang, Y. Hu, J.-H. He, Z.L. Wang,
SnO2 mixed nanowires via a single-step carbothermal reduction method,
Ultrahigh sensitive piezotronic strain sensors based on a ZnSnO3 nanowire/
Ceram. Int. 40 (2014) 5039–5042.
microwire, ACS Nano 6 (2012) 4369–4374.
[36] P. Sun, Y. Sun, J. Ma, L. You, G. Lu, W. Fu, M. Li, H. Yang, Synthesis of novel SnO2/
[8] B.K. Yun, Y.K. Park, M. Lee, N. Lee, W. Jo, S. Lee, J.H. Jung, Lead-free LiNbO3
ZnSnO3 core–shell microspheres and their gas sensing properties, Sens.
nanowire-based nanocomposite for piezoelectric power generation, Nanoscale
Actuators, B 155 (2011) 606–611.
Res. Lett. 9 (2014) 1–7.
[37] Y. Wu, R. Fan, P. Yang, Block-by-block growth of single-crystalline Si/SiGe
[9] S.A. Kelkar, P.A. Shaikh, P. Pachfule, S.B. Ogale, Nanostructured Cd2SnO4 as an
superlattice nanowires, Nano Lett. 2 (2002) 83–86.
energy harvesting photoanode for solar water splitting, Energy Environ. Sci. 5
[38] L. Fröberg, W. Seifert, J. Johansson, Diameter-dependent growth rate of InAs
(2012) 5681–5685.
nanowires, Phys. Rev. B 76 (2007) 153401.
[10] Z. Li, Y. Zhou, C. Bao, G. Xue, J. Zhang, J. Liu, T. Yu, Z. Zou, Vertically building
[39] J. Jie, G. Wang, G. Wang, X. Han, J. Fang, Q. Yu, Y. Liao, B. Xu, Q. Wang, J. Hou,
Zn2SnO4 nanowire arrays on stainless steel mesh toward fabrication of large-
Growth of ternary oxide nanowires by gold-catalyzed vapor-phase
area, flexible dye-sensitized solar cells, Nanoscale 4 (2012) 3490–3494.
evaporation, J. Phys. Chem. B 108 (2004) 8249–8253.
[11] T. Lim, H. Kim, M. Meyyappan, S. Ju, Photostable Zn2SnO4 nanowire transistors
[40] C. Pang, B. Yan, L. Liao, B. Liu, Z. Zheng, T. Wu, H. Sun, T. Yu, Synthesis,
for transparent displays, ACS Nano 6 (2012) 4912–4920.
characterization and opto-electrical properties of ternary Zn2SnO4 nanowires,
[12] Y.-Q. Jiang, C.-X. He, R. Sun, Z.-X. Xie, L.-S. Zheng, Synthesis of Zn2SnO4
Nanotechnology 21 (2010) 465706.
nanoplate-built hierarchical cube-like structures with enhanced gas-sensing
[41] S. Jun, G. Bing-Hui, C. Wei-Guo, L. Shu-Dong, Z. Zeng-Xing, L. Dong-Fang, L. Li-
property, Mater. Chem. Phys. 136 (2012) 698–704.
Feng, M. Wen-Jun, R. Yan, X. Yan-Juan, Synthesis and characterization of
[13] T.-Y. Ma, H. Li, T.-Z. Ren, Z.-Y. Yuan, Mesoporous SrTiO3 nanowires from a
axially periodic Zn2SnO4 dendritic nanostructures, Chin. Phys. B 17 (2008)
template-free hydrothermal process, RSC Adv. 2 (2012) 2790–2796.
2184–2190.
[14] M. Cao, Y. Wang, T. Chen, M. Antonietti, M. Niederberger, A highly sensitive
[42] Z. Cao, J.R. Stetter, A selective solid-state gas sensor for halogenated
and fast-responding ethanol sensor based on CdIn2O4 nanocrystals
hydrocarbons, Sens. Actuators, B 5 (1991) 109–113.
synthesized by a nonaqueous sol–gel route, Chem. Mater. 20 (2008) 5781–
[43] Z. Wen, L. Tian-Mo, Gas-sensing properties of SnO2/TiO2-based sensor for
5786.
volatile organic compound gas and its sensing mechanism, Physica B 405
[15] C.G. Read, Y. Park, K.-S. Choi, Electrochemical synthesis of p-type CuFeO2
(2010) 1345–1348.
electrodes for use in a photoelectrochemical Cell, J. Phys. Chem. Lett. 3 (2012)
[44] A. Sivapunniyam, N. Wiromrat, M.T.Z. Myint, J. Dutta, High-performance
1872–1876.
liquefied petroleum gas sensing based on nanostructures of zinc oxide and
[16] F. Koffyberg, F. Benko, Cd2SnO4, CdIn2O4, and Cd2GeO4 as anodes for the
zinc stannate, Sens. Actuators, B 157 (2011) 232–239.
photoelectrolysis of water, Appl. Phys. Lett. 37 (2008) 320–322.
[45] A.P. Lee, B.J. Reedy, Temperature modulation in semiconductor gas sensing,
[17] D. Chen, J. Xu, B. Liang, X. Wang, P.-C. Chen, C. Zhou, G. Shen, Electric transport,
Sens. Actuators, B 60 (1999) 35–42.
reversible wettability and chemical sensing of single-crystalline zigzag
[46] K.A. Ngo, P. Lauque, K. Aguir, High performance of a gas identification system
Zn2SnO4 nanowires, J. Mater. Chem. 21 (2011) 17236–17241.
using sensor array and temperature modulation, Sens. Actuators, B 124 (2007)
[18] B. Tan, E. Toman, Y. Li, Y. Wu, Zinc stannate (Zn2SnO4) dye-sensitized solar
209–216.
cells, J. Am. Chem. Soc. 129 (2007) 4162–4163.
[47] C. Wang, L. Yin, L. Zhang, D. Xiang, R. Gao, Metal oxide gas sensors: sensitivity
[19] Y. Su, L.-A. Zhu, L. Xu, Y. Chen, H. Xiao, Q. Zhou, Y. Feng, Self-catalytic formation
and influencing factors, Sensors 10 (2010) 2088–2106.
and characterization of Zn2SnO4 nanowires, Mater. Lett. 61 (2007) 351–354.
[48] B. Geng, C. Fang, F. Zhan, N. Yu, Synthesis of polyhedral ZnSnO3 microcrystals
[20] C.T. Cherian, M. Zheng, M.V. Reddy, B. Chowdari, C.H. Sow, Zn2SnO4 nanowires
with controlled exposed facets and their selective gas-sensing properties,
versus nanoplates: electrochemical performance and morphological evolution
Small 4 (2008) 1337–1343.
during Li-cycling, ACS Appl. Mater. Interfaces 5 (2013) 6054–6060.
[49] E. Oh, H.-Y. Choi, S.-H. Jung, S. Cho, J.C. Kim, K.-H. Lee, S.-W. Kang, J. Kim, J.-Y.
[21] Y.-F. Wang, K.-N. Li, Y.-F. Xu, H.-S. Rao, C.-Y. Su, D.-B. Kuang, Hydrothermal
Yun, S.-H. Jeong, High-performance NO2 gas sensor based on ZnO nanorod
fabrication of hierarchically macroporous Zn2SnO4 for highly efficient dye-
grown by ultrasonic irradiation, Sens. Actuators, B 141 (2009) 239–243.
sensitized solar cells, Nanoscale 5 (2013) 5940–5948.
[50] A.Z. Sadek, S. Choopun, W. Wlodarski, S.J. Ippolito, K. Kalantar-zadeh,
[22] Z. Chen, M. Cao, C. Hu, Novel Zn2SnO4 hierarchical nanostructures and their
Characterization of ZnO nanobelt-based gas sensor for H2, NO2 and
gas sensing properties toward ethanol, J. Phys. Chem. C 115 (2011) 5522–
hydrocarbon sensing, Sens. J., IEEE 7 (2007) 919–924.
5529.
[51] M. Yao, F. Ding, Y. Cao, P. Hu, J. Fan, C. Lu, F. Yuan, C. Shi, Y. Chen, Sn doped ZnO
[23] G. Ma, R. Zou, L. Jiang, Z. Zhang, Y. Xue, L. Yu, G. Song, W. Li, J. Hu, Phase-
layered porous nanocrystals with hierarchical structures and modified
controlled synthesis and gas-sensing properties of zinc stannate (ZnSnO3 and
surfaces for gas sensors, Sens. Actuators, B 201 (2014) 255–265.
Zn2SnO4) faceted solid and hollow microcrystals, CrystEngComm 14 (2012)
[52] D. Kohl, Function and applications of gas sensors, J. Phys. D: Appl. Phys. 34
2172–2179.
(2001) R125.
[24] S. Park, S. An, H. Ko, C. Jin, C. Lee, Enhanced NO2 sensing properties of Zn2SnO4-
[53] K.-W. Kim, P.-S. Cho, S.-J. Kim, J.-H. Lee, C.-Y. Kang, J.-S. Kim, S.-J. Yoon, The
core/ZnO-shell nanorod sensors, Ceram. Int. 39 (2013) 3539–3545.
selective detection of C2H5OH using SnO2–ZnO thin film gas sensors prepared
[25] L. Wang, X. Zhang, X. Liao, W. Yang, A simple method to synthesize single-
by combinatorial solution deposition, Sens. Actuators B123 (2007) 318–324.
crystalline Zn2SnO4 (ZTO) nanowires and their photoluminescence properties,
Nanotechnology 16 (2005) 2928–2931.
[26] Y.-C. Liang, C.-L. Huang, C.-Y. Hu, X.-S. Deng, H. Zhong, Morphology and optical
properties of ternary Zn–Sn–O semiconductor nanowires with catalyst-free
growth, J. Alloys Comp. 537 (2012) 111–116.