Applied Surface Science 542 (2021) 148555

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Applied Surface Science

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Full Length Article

Enhanced selective acetone gas sensing performance by fabricating

ZnSnO3/SnO2 concave microcube
Jintao Zhang , Xiaohua Jia *, Dandan Lian , Jin Yang , Sizhe Wang , Yong Li , Haojie Song *
School of Materials Science & Engineering, Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science &
Technology, Xi’an, Shaanxi 710021, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Unique ZnSnO3/SnO2 concave microcubes with different doping amount of SnO2 (5 wt%, 10 wt%, 15 wt%) were
ZnSnO3/SnO2 obtained by a simple hydrothermal reaction. A sequence of experiments based on different ratios of
Concave microcubes Na3C6H5O7⋅2H2O and SnCl4⋅5H2O were carried out, exploring the reason for the formation of concave micro­
Oxygen vacancies
cube. Many SnO2 nanoparticles were densely anchored on the rough surface of the as-obtained concave
Gas sensing
microcubes, which further increased the specific surface area and provided more active sites for the adsorption-
Acetone
desorption of gas molecules, delivering outstanding gas sensing performances. A high gas sensing response value
(18.3), fast response/recovery time (5/6 s), good reproducibility and selectivity as well as extraordinary stability
have been recorded in the case of ZnSnO3/10 wt%SnO2 composites. In comparison with the pure ZnSnO3 and
ZnSnO3/SnO2 sensors with other ratios (5 wt%, 15 wt%), the ZnSnO3/10 wt%SnO2 sensor displayed a distinct
enhancement in gas sensing properties toward acetone, which can be owed mainly to increased high surface to
volume ratios, the presence of oxygen vacancies and the synergistic effect between ZnSnO3 and SnO2.

1. Introduction
Recently, gas-sensing materials received increased attention due to
the growing emission of volatile organic compounds (VOCs) and toxic
gases released from daily life and industrial activities [1-3]. Acetone, as
one of the most relevant VOCs, is flammable, explosive, and toxic. High
concentrations of acetone in the air could be harmful to (human) health
and could cause damage to other properties as well. Therefore, real-time
monitoring of acetone could play a vital role in ensuring people’s safety.
High sensitivity, fast response, excellent selectivity, and long-term sta­
bility are essential parameters of high-sensitivity gas sensors [4,5]. In
order to satisfy these parameters, many investigations are focusing on
the shape-tailoring of materials, including regular nanoparticles [6],
nanobelts [7,8], nanoflowers [9], nanowires [10], nanocubes [11], core-
shell structures [12]. Among them, cubes (as a polyhedral morphology)
with sharp edges and tips possess the relatively large surface to volume
ratio and external contact areas, which could provide more active sites
and abundant diffusion paths for gas adsorption-desorption as well as
could facilitate the transfer of charge carriers on the surface [13].
Therefore, using cube-like morphology can significantly enhance the
gas-sensing performances of a device/material [14-16].
Metal oxide semiconductors (MOSs), such as ZnO [17], SnO2 [4,18],
Fe2O3 [12], CuO [19] and ZnSnO3 [20] have been extensively used for
detection of acetone, owing to their advantages in terms of high sta­
bility, enhanced cost-efficiency, and excellent gas-sensing properties.
Among these MOSs, ZnSnO3, as an outstanding candidate for gas
detection, which had the high chemical sensibility and excellent elec­
trical performance, has been widely used in gas sensors [21]. The spatial
arrangement of atoms in ZnSnO3 is an octahedron. Due to its particular
crystal structure, ZnSnO3 could possess many oxygen vacancies (VOs) to
provide more adsorption positions of oxygen, which can promote the
reactivity with the reducing gas, leading to enhanced gas-sensing per­
formances [21]. Many investigations have been focused on the single
component ZnSnO3 cube structures as gas-sensing materials. Huang
et al. obtained porous ZnSnO3 cubes by a cost-efficient approach, using
an aqueous solution method, and subsequent calcination, showing a
good response (16) to 100 ppm acetone at 300 ◦ C [15]. Zhou et al.
synthesized ZnSnO3 hollow and multihulled cubes, displaying enhanced
performances in gas sensing [22,23]. Zeng et al. prepared novel ZnSnO3-
based hollow cubic nanocages by a facile one-pot hydrothermal route,
exhibiting a high response to formaldehyde [24].
Although significant advances have been made in gas-sensing of the

* Corresponding authors.
E-mail addresses: xhjia2003@126.com (X. Jia), songhaojie@sust.edu.cn (H. Song).

https://doi.org/10.1016/j.apsusc.2020.148555
Received 11 June 2020; Received in revised form 25 October 2020; Accepted 19 November 2020
Available online 29 November 2020
0169-4332/© 2020 Elsevier B.V. All rights reserved.
J. Zhang et al.
Fig. 1. The synthesis process of ZnSnO3/SnO2 concave microcubes.
single-component cubes, the higher gas-sensing performance based on
multi-component microcube structures has aroused increasing interest.
Some researchers reported the synthesis of multi-component micro­
cubes, such as Pt/CdIn2O4 cube [25], Cu-doped α-Fe2O3 cubes [16], Pd-
doped SnO2 hollow microcubes [26], Cu2O/CuO cubes [27], CuO@ZnO
microcubes [28] and Zn2SnO4/SnO2 cubes [29]. These hybrid (micro)
structures have usually shown enhanced gas-sensing characteristics than
the single-components. Thus, the multi-component materials have
become a widespread approach for obtaining excellent gas sensing
performances [30]. Furthermore, SnO2, as a superior gas sensing ma­
terial and a right candidate for doping material, could be obtained in the
form of different SnO2 nanostructures (nanoparticles, nanowires,
flower-like nanorods etc.) [31,32]. Thus, ZnSnO3 integrated with SnO2
could be considered to be a feasible way to obtain high-performance gas
sensing devices.
Herein, the ZnSnO3/SnO2 concave microcubes with different
amounts of doping agent (SnO2) were fabricated using a facile liquid
phase method. As-fabricated ZnSnO3 hollow microspheres and ZnSnO3/
SnO2 concave microcubes were assembled into gas sensors for the
detection of VOCs. The effects of different amounts of SnO2 doping agent
on the structures, morphologies, and gas sensing characteristics of
ZnSnO3 were also studied. The results showed the ZnSnO3/10 wt%SnO2
concave microcube sensor displayed outstanding gas sensing properties
with a high gas sensing response (18.3), fast response/recovery time (5/
6 s), good selectivity and high operational stability in the presence of
acetone at 260 ◦ C. These performances were attributed to the significant
synergistic effect in ZnSnO3/SnO2 hybrid, a large number of oxygen
vacancies were generated to guarantee efficient electron transport and
to provide abundant space for gas adsorption-desorption. Besides, a gas-
sensing mechanism of ZnSnO3/SnO2 concave microcubes was proposed
to explain the enhanced gas sensing properties.
2. Experimental
2.1. Preparation of ZnSnO3/SnO2 concave microcubes
ZnSnO3/SnO2 concave microcubes with different amounts of SnO2
doping agent (5 wt%, 10 wt%, 15 wt%) were prepared by a simple
liquid-phase reaction. In the first step, ZnSnO3 hollow microspheres
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Applied Surface Science 542 (2021) 148555
were obtained by in-situ precipitation method in an oil bath at 80 ◦ C for
3 h [20]. A typical experiment for the synthesis of the ZnSnO3/10 wt%
SnO2 concave microcube composites could be described as follows: 0.5 g
of the obtained ZnSnO3 powders were dispersed in 30 mL water-alcohol
solution (volume ratio 2:1) with vigorous stirring (denoted suspension
A). Afterward, 0.097 g of Na3C6H5O7⋅2H2O was directly dissolved in
suspension A. Meanwhile, SnCl4⋅5H2O (0.116 g) and NaOH (0.0792 g)
were dissolved in the water-alcohol solution by stirring for 10 min,
respectively (denoted solution B, C). Then, solutions B and C were suc­
cessively added dropwise to the suspension A. After stirring again for 10
min, the suspension was transferred to a 100 mL autoclave and main­
tained at 120 ◦ C for 12 h. The obtained reaction product was cleaned by
alternately centrifugal washing with ethanol and deionized water, fol­
lowed by drying at 70 ◦ C in an oven. The synthesis process of the
concave microcubes can be observed in Fig. 1. In order to evaluate the
influence of different amounts of SnO2 (5 wt%, 15 wt%) on the
morphology and gas sensing performances of ZnSnO3/SnO2 composites,
the same procedure was followed, adjusting the quantities of SnO2. The
amounts of specific reagents are listed in Table SI1.
2.2. Characterization
The as-synthesized samples were characterized by X-ray diffraction
(XRD, D8 Advance, Bruker, Germany) with Cu-Kα radiation, field
emission scanning electron microscopy (FE-SEM, S4800, JEOL Ltd.,
Japan), transmission electron microscopy (TEM, JSM-2100plus, JEOL
Ltd., Japan), static volumetric analysis (TriStar II 3020, Micromeritics,
USA), X-ray photoelectron spectrometry (XPS, VG ESCALAB 210, VG
Scientific, USA) and Photoluminescence spectra (PL, FS5, Edinburgh).
2.3. Gas-sensing measurement
The gas-sensing performances of ZnSnO3/SnO2 concave microcubes
were tested by a commercial WS-30A static gas sensing measurement
system (Zhengzhou Winsen Electronics Technology Co. Ltd., China). The
schematic illustration of ZnSnO3/SnO2 based hybrid gas sensors was
displayed in Fig. SI1. The as-obtained powders with appropriate
amounts of deionized water were mixed and ground to form a homog­
enous paste for coating. The outer surface of ceramic tubes was dip-
J. Zhang et al.
Fig. 2. (a-d) SEM and (e-h) TEM images of ZnSnO3 hollow microspheres and ZnSnO3/SnO2 concave microcubes with different amounts of SnO2 (5 wt% (b, f), 10 wt%
(c, g), 15 wt% (d, h)). The inset in (a) represents a high-magnification SEM micrograph of ZnSnO3 hollow microspheres. The inset in (f, g, h) are high-magnification
TEM images of ZnSnO3/SnO2 composites. (i) The SEM image of ZnSnO3/10 wt%SnO2 concave microcube. (j, k, l) EDS elemental mapping images of Zn, Sn and O.
coated in the mixtures, then heat-treated in an oven at 200 ◦ C for 2 h.
After aging (220 ◦ C) for 10 days, the gas sensors were tested using a
static measurement system.
The gas response (S) was defined by the equation (S = Ra/Rg = Vg/
Va), where R (Ra, Rg) and V (Va, Vg) were the resistance and voltage
values of the gas sensors in air and target gas. The response-recovery
time was considered as the time at which the total resistance reached
ninety percent of adsorbed and desorbed gas. During testing, the
working temperature was controlled by adjusting the heating voltage,
while the test data was automatically collected by a computer connected
to the sensing tester.
3. Results and discussion
3.1. Structural and morphological characterizations
The results of morpho-structural investigations of ZnSnO3 hollow
microspheres and ZnSnO3/SnO2 composites were presented in Fig. 2(a-
h). The ZnSnO3 hollow microspheres with an average diameter of 1–1.3
μm have a relatively homogeneous morphology, being also well
dispersed. The high-magnification SEM micrograph of broken micro­
spheres (inset in Fig. 2(a)) verifies the formation of the hollow structure,
which is also found on the rough surface, consisting of small ZnSnO3
nanoparticles. The bright contours further show the hollow structure
around the inner part of the microspheres (Fig. 2(e)), which is in
agreement with the results of SEM. The morphologies of ZnSnO3/SnO2
concave microcubes with different amount of SnO2 (5 wt%, 10 wt%, 15
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Applied Surface Science 542 (2021) 148555
wt%) were shown in Fig. 2(b-d) and Fig. SI2. SEM and TEM images
display that SnO2 nanoparticles are well anchored on the surface of
ZnSnO3/SnO2 concave microcubes. As demonstrated in Fig. SI3(a), the
characteristic peaks of SnO2 appeared in the XRD pattern of the nano­
composite, further proving the existence of SnO2. The HRTEM image of
the interfaces between ZnSnO3 and SnO2 for ZnSnO3/10 wt%SnO2
concave microcubes was provided in Fig. SI4 and the clear lattice fringes
can be observed with a lattice spacing of 0.34 nm corresponding to the
crystal plane of SnO2 (1 1 0), which further demonstrates that the
nanoparticles distributed on the surface of the concave microcube are
SnO2. However, due to the large size of ZnSnO3, it is difficult to observe
its lattice fringes. In addition, it can be seen from Fig. SI2 that the
average sizes of ZnSnO3/SnO2 concave microcubes (5 wt%, 10 wt%, 15
wt%) are around 2.65 μm, 2.32 μm, and 2.13 μm, respectively, indi­
cating that the size of microcubes decrease with the increase of SnO2
doping amount. When the doping amount of SnO2 is 5 wt%, the sparse
SnO2 is anchored on the surface of the microcube. As the amount of
doping agent increases to 10 wt%, a microcube-like concave structure is
formed, and SnO2 nanoparticles are uniformly anchored on its surface.
When the amount of SnO2 increases to 15 wt%, the concave structure of
microcubes becomes more visible, and the excessive doping of SnO2
causes a surface disorder, increasing the surface density and reducing
the gas sensitivity. The elements and element distribution of ZnSnO3/10
wt%SnO2 concave microcubes were studied by EDX (Fig. SI3(b)) and
EDS (Fig. 2(j-l)). Fig. SI3(b) reveals that only Zn, Sn and O existed in the
composites. The EDS elemental mapping of the selected ZnSnO3/10 wt%
SnO2 concave microcube (Fig. 2(i)) could be consulted in Fig. 2(j-l),
J. Zhang et al. Applied Surface Science 542 (2021) 148555

Fig. 3. Typical SEM images of products from ZnSnO3 hollow microspheres to ZnSnO3/10 wt%SnO2 concave microcubes at different substance ratios of
Na3C6H5O7⋅2H2O and SnCl4⋅5H2O (a) 0:0, (b) 1:0, (c) 0:1, (d) 1:4, (e) 1:2, (f) 1:1.

further indicating the coexistence and uniform distribution of Zn, Sn,
and O in the ZnSnO3/SnO2 composites.
In order to investigate the formation processes of ZnSnO3/SnO2
concave microcubes, a sequence of controlled experiments was per­
formed. Fig. 3 presents the typical SEM images of products starting
ZnSnO3 hollow microspheres to ZnSnO3/10 wt%SnO2 concave micro­
cubes, using different substance ratio of Na3C6H5O7⋅2H2O and
SnCl4⋅5H2O. In the first case, Fig. 3(a) shows the hollow microspheres of
the as-obtained sample, which revealed that the hollow microspheres
structure was a basal body in the evolution processes of ZnSnO3/10 wt%
SnO2 concave microcubes. When the substance ratio of
Na3C6H5O7⋅2H2O and SnCl4⋅5H2O was 1:0 in the reaction solution, the
as-obtained sample still kept the hollow structure in Fig. 3(b), but had a
rougher surface, suggesting the surface activity could be a function of
Na3C6H5O7⋅2H2O. When the substance ratio changed to 0:1, the smooth
microcube shape was formed (Fig. 3(c)), which was completely different
from the original hollow microsphere structure of ZnSnO3, indicating
that the presence of SnCl4⋅5H2O could create a suitable environment to
initiate a crystallization process. The transformation of the morphology
in this process could be explained by the mechanism of nucleation-

Fig. 4. XPS spectra of ZnSnO3/10 wt%SnO2 concave microcubes: (a) a survey spectrum, high resolution spectra for (b) Zn 2p, (c) Sn 3d, (d) O 1s (of ZnSnO3), (e) O 1s
(of ZnSnO3/10 wt%SnO2), (f) fitting results of O 1s XPS spectra of ZnSnO3 and ZnSnO3/10 wt%SnO2.

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J. Zhang et al. Applied Surface Science 542 (2021) 148555

Fig. 5. (a) Response of ZnSnO3 hollow microspheres and ZnSnO3/SnO2 composites sensors in the presence of 50 ppm acetone under different operating temper­
atures. (b) The response of ZnSnO3 and ZnSnO3/SnO2 composites sensors in the presence of 50 ppm different VOCs at 260 ◦ C. (c, d) Voltages and response-recovery
cycles of semiconductor-based sensors towards 1–600 ppm of acetone at 260 ◦ C. (e) Response-recovery curves of sensors in the presence of acetone (50 ppm). (f)
Response values of gas sensors calculated from Fig. (e). (g) Long-term stability (49 days) of ZnSnO3/10 wt%SnO2 sensor towards 50 ppm acetone at 260 ◦ C.

dissolution-recrystallization [33]. More importantly, it is noteworthy
that SnO2 nanoparticles were not grown on the surface of microcubes as
expected when no Na3C6H5O7⋅2H2O was added. Thus, it could be
affirmed that Na3C6H5O7⋅2H2O plays a crucial role in the growth of
SnO2 nanoparticles on the surface of the concave microcubes. Different
substance ratios of Na3C6H5O7⋅2H2O and SnCl4⋅5H2O were also added
to the reaction solution in order to control the reaction parameters
further. As shown in Fig. 3(d-f), with the increase of Na3C6H5O7⋅2H2O,
more SnO2 nanoparticles were anchored on the surface of microcubes,
and the sample displayed well defined concave microcubes. These ob­
servations indicated that Na3C6H5O7⋅2H2O could play a significant role
not only in the growth of SnO2 nanoparticles on the surface of concave
cubic microstructures, but also in the formation of these concave cubic
structure.
Based on these experimental results, the formation process probably
involved the following two steps. In the first step, the Na3C6H5O7⋅2H2O,
as surface modifier, changed the surface of ZnSnO3 hollow microspheres
rougher and worked synergistically with SnCl4⋅5H2O to promote the
transformation of hollow spheres into microcubes. In the second step,
under the OH− conditions of tetravalent tin ions, the nucleation of SnO2
appeared on the surface of the microcubes, which promoted the for­
mation of the concave structures. Finally, the ZnSnO3/SnO2 concave
microcubes were formed from ZnSnO3 hollow microspheres by intro­
ducing Na3C6H5O7⋅2H2O and SnCl4⋅5H2O in an alkaline condition.
In order to study the elemental composition and chemical proper­
ties/states of ZnSnO3/10 wt%SnO2 concave microcubes, XPS measure­
ments were performed (Fig. 4). A total spectrum of Zn, Sn, and O was
investigated (Fig. 4(a)) in the case of ZnSnO3/10 wt%SnO2 composites.

5
J. Zhang et al.
Fig. 4(b) depicts the high-resolution spectrum of Zn 2p, being divided
into two photoelectron peaks: Zn 2p3/2 (located at 1021.88 eV) and Zn
2p1/2 (located at 1044.98 eV). The high-resolution spectrum of Sn 3d
was also divided into two photoelectron peaks (Fig. 4(c)): Sn 3d5/2
(located at 486.78 eV) and Sn 3d3/2 (located at 495.18 eV). The bimodal
spin-orbit displayed a split value of around 8.4 eV, suggesting the
presence of Sn4+ cations [34]. The O 1s spectra of ZnSnO3 and ZnSnO3/
10 wt%SnO2 composites are shown in Fig. 4(d) and (e), which is divided
into three fitted peaks, ascribed to the three significant oxygen species
[35], represented as OL, OV, OC, corresponding to the O2− species in the
lattice, VOs, and chemisorbed or dissociated oxygen species, respec­
tively [36]. The three peaks of the ZnSnO3 hollow microspheres were
located at 529.99 eV, 531.12 eV, 532.23 eV, while those of ZnSnO3/10
wt%SnO2 concave microcubes were situated in 529.99 eV, 531.33 eV,
and 532.27 eV, peaks which could be assigned to the presence of OL, OV,
OC species, respectively. It has to be noted that the gas sensing properties
could be highly related to the presence of VO species on the surface of
the semiconductor [30]. Meanwhile, the relative percentage of each
oxygen species in ZnSnO3 and ZnSnO3/10 wt%SnO2 composites were
collected in Fig. 4(f). It is clear that the percentage of OV of ZnSnO3/10
wt%SnO2 concave microcubes substantially increased in comparison
compared with that of SnO2-free ZnSnO3 hollow microspheres, which
could be considered a promising parameter to obtain good gas sensing
performance for these microstructures.
In order to further explore the oxygen vacancies in the samples, the
photoluminescence (PL) spectra were performed as shown in Fig.SI5. All
peaks of ZnSnO3-based composites appear at around 530 nm, which is
attributed to the presence of oxygen vacancies in the ZnSnO3-based
composites [37]. With the increase of SnO2 doping amounts, the in­
tensity of PL peak (530 nm) first increases and then decreases. Notably,
the ZnSnO3/10 wt%SnO2 concave microcubes display the highest PL
peak, indicating that the ZnSnO3/10 wt%SnO2 sample possesses the
more oxygen vacancies than those of other ZnSnO3-based samples
[37,38].
Fig. SI6 presents the N2 adsorption-desorption isotherms and the
corresponding pore size distribution of the ZnSnO3-based microstruc­
tures. As shown in Fig. SI6(a), ZnSnO3 hollow microspheres and
ZnSnO3/SnO2 concave microcubes with different doping amount dis­
played a type IV isotherm with an H3-type hysteresis loop in a relative
pressure (P/P0) of 0.5–1. Meanwhile, the pore size distributions (Fig. SI6
(b)) showed correspondingly the maximum peak of pore size of samples,
listed in Table SI2. It has to be mentioned that ZnSnO3/10 wt%SnO2
concave microcubes possessed the largest specific surface area (69.7 m2/
g) in comparison with ZnSnO3 hollow microspheres (40.7 m2/g) and
other ZnSnO3/SnO2 composites (5 wt% (57.4 m2/g) and 15 wt% (64.5
m2/g)). The maximum peak pore diameter of ZnSnO3/10 wt%SnO2
concave microcubes (around 9.0 nm) was also larger than the other
three samples. It is suggested that the more accentuated mesoporous
structure combined with a higher specific surface area of ZnSnO3/SnO2
concave microcubes could enhance the gas sensing properties of
microstructures.
3.2. Gas-sensing performances
As it is already known, the change in the operating temperature can
highly affect the gas sensing properties of the sensing material. To verify
it, the responses of as-fabricated ZnSnO3 and ZnSnO3/SnO2 composites
sensors in the presence of 50 ppm acetone were performed under
different temperatures (Fig. 5(a)). It can be affirmed that in the case of
all gas sensors, as the working temperature increased, the responses
towards acetone showed an increased tendency before reaching the
optimal response/maximum at 260 ◦ C, and then the response decreased
with the continuous decrease of the working temperature. Therefore,
260 ◦ C was selected as the optimum operating temperature. At 260 ◦ C,
the acetone response of ZnSnO3 hollow microspheres was 9.1, while the
responses of ZnSnO3/SnO2 composites with different amounts of SnO2
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Applied Surface Science 542 (2021) 148555
(5 wt%, 10 wt% and 15 wt%) were 10.9, 18.3, 11.9. Notable, ZnSnO3/
10 wt%SnO2 concave microcubes displayed 2 times enhancement in its
response toward acetone response in comparison with the “pure”
ZnSnO3 hollow microspheres, which further verified the enhancing ef­
fect of SnO2 nanoparticles and the high sensitivity of concave micro­
cubes nanostructure toward acetone.
Furthermore, selectivity is another essential operating parameter
when the applicability of a gas sensor is evaluated. The gas-sensing
performances of the semiconductors were evaluated by exposing them
to 50 ppm exposing different VOCs (Fig. 5(b)), including toluene,
methanol, ammonia, ethanol and acetone at 260 ◦ C. The responses of
ZnSnO3/SnO2 composites were superior in comparison with the results
shown by ZnSnO3 hollow microspheres. Moreover, the ZnSnO3/10 wt%
SnO2 concave microcubes exhibited the optimal response to each gas
and displayed the highest sensitivity towards acetone. These results
could be mainly attributed to the increased amount of oxygen vacancies
and surface area, as shown by XPS and BET.
Fig. 5(c, d) displays the dynamic response-recovery cycles of as-
assembled sensors towards in a concentration range of 1–600 ppm of
acetone at 260 ◦ C. As the concentration increased, the responses of gas
sensors increased gradually, and the current responses repeatedly
regained the initial baseline, suggesting an excellent reproducibility.
The ZnSnO3/SnO2 composite gas sensors showed a higher response to
acetone in comparison with the ZnSnO3 hollow microspheres. With the
increase amount of SnO2, the response increased first, reaching a
maximum at 10 wt%, while at higher concentration (15%), the response
decreased, revealing that the already mentioned 10 wt% could be the
optimal doping ratio of SnO2. Besides, the response of gas sensors
gradually increased with the increase of acetone concentration. More­
over, at all of the concentration, the response of ZnSnO3/SnO2 concave
microcubes was higher than those of ZnSnO3 hollow microspheres,
which further confirmed the advantages of as-obtained concave micro­
cube structures. The details of the relevant data are displayed in Fig. SI7.
As the concentration of the acetone increased, the current response
repeatedly regained to the original baseline. In Fig. SI8, the resistance
curves of ZnSnO3 and ZnSnO3/SnO2 were evaluated by purging in and
out 1–600 ppm acetone through multiple cycles. In the first instance, it
could be observed that all sensors displayed typical n-type gas-sensing
behavior. As the doping amount of SnO2 increased, the resistances of
ZnSnO3/SnO2 composites gradually decreased, indicating an electronic
interaction between ZnSnO3 and SnO2 nanoparticles. This interaction
could be mainly attributed to the charge transfer caused by Van der
Waals forces or to the modulation of the Schottky barrier between
ZnSnO3 and SnO2 [39]. Moreover, the resistance curves of ZnSnO3/SnO2
composite were stable over multiple cycles while the resistance curve of
ZnSnO3 displayed significant vibrations/changes during acetone on/off
cycling, exhibiting once more the outstanding stability of ZnSnO3/SnO2
composites for gas-sensing.
In practical applications, it is usually required that the high-
performance gas sensors possess excellent response-recovery charac­
teristics to the target gases. The response-recovery times are measured
as the time when the resistance of the adsorbed and desorbed gas
reached ninety percent. Upon exposure to the acetone atmosphere, the
sensors first responded and then remained steady. The purging of clean
air led to the recovery of the initial state of the sensor, indicating good
reversibility. Fig. 5(e) depicts the response and recovery curves of
ZnSnO3 and ZnSnO3/SnO2 composites towards 50 ppm acetone
(260 ◦ C). The response-recovery times of ZnSnO3 and ZnSnO3/SnO2
composite based gas sensors towards acetone were determined as 12/27,
10/9, 5/6 and 8/13 s, respectively. It was observable that the response
and the recovery speed of ZnSnO3/10 wt%SnO2 concave microcubes
were better than those of “pure” ZnSnO3 hollow microsphere and
ZnSnO3/SnO2 composites with other concentrations (5 wt% and 15 wt
%). Meanwhile, it can be seen from Fig. 5(c) that the curves of ZnSnO3/
SnO2 composites ascended or descended faster than the ZnSnO3 curve
when acetone was in or out, indicating the better response-recovery
J. Zhang et al. Applied Surface Science 542 (2021) 148555

Table 1 the concentration and mobility of the charge. SnO2 is a well-known n-

The gas-sensing performance of ZnSnO3/10 wt%SnO2 concave microcubes in type semiconductor, characterized by its high free charge density. Thus,
the presence of acetone, compared with some previously reported gas sensors. the gas sensing mechanism of ZnSnO3/SnO2 concave microcubes (as
Materials Concentration Operating Response References shown in Fig. 6) can be simply understood as the surface-controlled
(ppm) temperature (Ra/Rg) mechanism, and the change of resistance depends on the species and
(◦ C) the amount of chemisorbed oxygen on the surface. In ambient air, the
ZnSnO3 100 280 5.5 [20] resistance of ZnSnO3/SnO2 concave microcubes is mainly controlled by
ZnO/SnO2 5 350 14.13 [34] the concentration of the adsorbed oxygen species (O−2 , O− and O2− ) by
ZnSnO3/ 50 280 17.03 [35]
capturing the free electrons from the conduction band of the SnO2, as
SnO2
SnO2/Fe2O3 200 270 9.3 [40] illustrated in equation (1) [46]. In this process, the adsorbed oxygen
SnO2/WO3 100 360 12.1 [41] species create an electron depletion layer (EDL) due to the electrons
SnO2/WO3 100 300 6 [42] transfer from the ZnSnO3/SnO2 to oxygen, which could lead to the initial
CuO/SnO2 50 250 1.11 [19] high resistance of the material. When gas sensors are exposed to acetone,
SnO2-Sn-0.5 100 250 10.91 [43]
Au@SnO2/ 100 300 16 [44]
the reaction between acetone molecules and surface-adsorbed oxygen
Fe2O3 species (described by equation (2) [47]) releases the captured electrons
NiO/SnO2 100 240 10.1 [45] back to the conduction band, which increases the concentration of the
ZnSnO3/10 50 260 19.1 This work electrons and decreases the thickness of the EDL, causing a decreasing
wt%SnO2
resistance of the sensors.

O2 (gas) ↔ O2 (ads) O2 + e− →O− , O−2 , O2− (1)

characteristic of composite sensor.
The long-term stability of ZnSnO3/10 wt%SnO2 concave microcubes
gas sensor was also investigated (Fig. 5(g)). The response to acetone (50
ppm) was stable for 49 days with a slight variation of less than 3%,
indicating outstanding long-term stability. To further evaluate the gas
sensitivity features, the obtained results were compared to those of
ZnSnO3 and SnO2 based gas sensors (Table 1). Compared with the pre­
viously investigated sensors [19,20,34,35,38-43], the synthesized
ZnSnO3/10 wt%SnO2 concave microcubes displayed superior sensitivity
towards acetone, with enhanced applicability prospects.
3.3. Gas-sensing mechanism
The gas sensing characteristics of MOS based sensors could be
derived from the changes in resistance, which is mainly determined by
CH3COCH3 (ads) + 8O2− (O−2 , O− ) (ads) → 3CO2 (ads) + 3H2O (ads) +
16e− (2)
Compared to ZnSnO3 hollow microspheres, the ZnSnO3/10 wt%
SnO2 composites had more Vos with a percentage of 77.96%, which is
nearly three-fold higher than that of ZnSnO3 hollow microspheres, being
benefic for improving the sensitive performance of gas-sensing materials
[48]. Meanwhile, it was also supposed that SnO2 plays an important role
in activating the dissociation rate of molecular oxygen during the
“chemical sensitization” mechanism established by the spillover effect
[26]. However, an excessive ratio of SnO2 could cause surface disorder
and increase the surface state density, which gives rise to the pining of
surface Fermi level and could reduce the response of gas sensors [49].
Based on this, the optimal doping ratio of SnO2 (10 wt%) was further

Fig. 6. Schematic diagram of the gas sensing mechanism of ZnSnO3/SnO2 concave microcubes.

7
J. Zhang et al.
confirmed by the results of the gas sensing measurement.
The high response and fast response-recovery speed of ZnSnO3/10 wt
%SnO2 composite are mainly based on the concave microcube structure,
which owns an increased surface to volume ratio and specific surface
area. For one thing, the homogeneous, dispersive concave microcubes
could avoid the aggregation of gas-sensing materials. Moreover, the
larger pore sizes and higher specific surface area (listed in Table SI1)
could provide more efficient gas diffusion and more reactive sites of gas-
sensing materials. Thus, efficient gas diffusion and enough reactive sites
could be responsible for enhancing the gas-sensing performances of gas
sensors. Furthermore, the synergic electronic interaction effects be­
tween SnO2 (3.8 eV) and ZnSnO3 (5.3 eV) cannot be neglected, as the
difference in their band gaps could significantly reduce the recombi­
nation rate of trapped electrons and generated holes and can accelerate
more electrons to be transferred effectively from the electron releasing
reaction of Equation (2) to the surface of the ZnSnO3/10 wt%SnO2
composites. After that, the conductivity of the sensing material is
remarkably increased, leading to high response.
4. Conclusions
ZnSnO3/SnO2 concave microcubes with different doping amount of
SnO2 were prepared by a simple solution method. SEM and TEM showed
that ZnSnO3/SnO2 concave microcubes had diameters of 2.3 ± 0.3 μm,
and many SnO2 nanoparticles were successfully grown on the surface of
ZnSnO3 hollow microspheres. A series of controlled experiments in
different ratios of Na3C6H5O7⋅2H2O and SnCl4⋅5H2O were conducted to
elucidate the formation mechanism of ZnSnO3/SnO2 concave micro­
cubes. Compared with the other three sensors, the ZnSnO3/10 wt%SnO2
sensor possessed the highest response toward acetone (19.1), fast
response/recovery time (4/6 s), good reproducibility and long-term
stability. The enhanced gas-sensing performances of ZnSnO3/10 wt%
SnO2 composites could be mainly attributed to sufficient oxygen va­
cancies, high specific surface area and synergistic effect between SnO2
and ZnSnO3. The results confirmed that ZnSnO3/10 wt%SnO2 concave
microcubes could have an outstanding potential candidate for acetone
detection.
CRediT authorship contribution statement
Jintao Zhang: Writing - review & editing, Software. Xiaohua Jia:
Conceptualization, Data curation, Validation, Funding acquisition. : .
Dandan Lian: Investigation, Methodology. Jin Yang: Investigation.
Sizhe Wang: Software. Yong Li: Visualization. Haojie Song: Supervi­
sion, Resources, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work is supported by the National Natural Science Foundation
of China (No. 51875330 and 51975342), and the Natural Science
Foundation of Shaanxi Province (No. 2018JZ5003 and 2019JZ-24).
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