Sensors & Actuators: B.

Chemical 364 (2022) 131876

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Sensors and Actuators: B. Chemical

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

Recent advances in SnO2 nanostructure based gas sensors

Yoshitake Masuda
National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560, Japan

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

Keywords: The detection of low-concentration gases and odors in fields such as healthcare, mobility, and indoor environ­
Gas sensor ment control is attracting tremendous attention. The development of high-sensitivity gas sensors capable of
Odor sensor detecting low concentrations of gases and molecules is strongly desired. This review focuses on tin oxide
SnO2
nanomaterials, which are substances that are being actively researched as semiconductor-type gas sensors. In
Nanostructure
Tin oxide
particular, the development of novel tin oxide nanomaterials over the last decade and their gas sensing appli­
cations are discussed. It is revealed that dimension and morphology affect the sensing performance. Tin oxide
nanomaterials having nano-meter size which is similar to size of a depletion layer, and controlled microstructure
such as a nanosheet structure shows high sensing performance. The dendritic structure in which 2D nanosheets
are connected by crystal growth points the direction for future sensor development. Furthermore, the high gas
adsorption performance and reactivity of the metastable crystal plane will be a guide for future sensor
development.

1. Introduction development of taste sensors and odor sensors must be focused on

The five basic human senses—eyesight, hearing, touch, taste, and
smell—are important for collecting information. Electronic devices that
imitate the functions of these five senses have been developed for de­
cades. Among these senses, eyesight is the most developed. Image sen­
sors and video cameras have been widely used for capturing moving
images. Telephoto, high-speed, and infrared cameras have more func­
tions than those of human eyesight. In addition, information processing
technology is applied as a brain substitute to analyze the image data and
to recognize objects and situations. Moreover, image recognition based
on artificial intelligence (AI) technology has also made remarkable
progress. Hearing is also being imitated by electronic devices, such as
recording devices, which conveniently record audio data, and acoustic
and ultrasonic sensors. Moreover, voice information processing and
recognition technologies are being developed using AI. Visual and
auditory imitation devices are at the technical level of sensing as well as
information processing and recognition. Judgment technology based on
information recognition has also been developed in combination with
AI. Force sensors, slip sensors, and proximity sensors have been devel­
oped as touch-imitation devices. Force sensors are the basis of touch
sensors and can detect pressure, torque, and direction. Slip sensors can
detect the speed and degree of slip between an object and a sensor.
Proximity sensors can detect distances to noncontact objects and are
more functional than the human touch sense. However, the
because of the difficulties involved in their fabrication compared to that
of other sensors.
A taste sensor containing lipid/polymer receptors is commercially
available, in which taste is quantified using the output potentials from
the receptors (Taste sensor TS-5000Z, Irie Corporation.) [1,2]. However,
aspects such as high-speed sensing, continuous monitoring, miniaturi­
zation, and cost reduction must be accomplished for taste sensors
compared to visual and auditory sensors.
The development of odor sensors is crucial because of their possible
applications for various purposes. Odor sensors have been extensively
used to detect gas leakage and in fields such as healthcare, mobility, and
spatial environment control, in which the detection of low-
concentration biogas and odor is crucial [3]. However, sensors that
can detect high-concentration gas leaks cannot analyze
low-concentration odors, which requires the development of sensors
with higher sensitivities. In addition, most odor components have a
larger molecular weight than that of gas molecules in gas leakage
detection. Moreover, certain odors are mixtures of multiple molecules,
and the coexisting molecules and water vapor behave as contaminant or
noise gases during detection of the target molecules. Therefore, the
identification of target molecules even in the presence of these
contaminant gases is critical. Sensing technology is advancing rapidly
with the internet of things (IoT) technology. Constant monitoring using
numerous sensors at various locations is a possible reality in the future,

E-mail address: masuda-y@aist.go.jp.

https://doi.org/10.1016/j.snb.2022.131876
Received 9 February 2022; Received in revised form 5 April 2022; Accepted 9 April 2022
Available online 15 April 2022
0925-4005/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Y. Masuda
which necessitates the development of odor sensors that are compact,
cost-effective, vibration-resistant, stable against temperature fluctua­
tions, durable against ultraviolet rays and drying, and exhibiting
long-term stability and reliability.
Nikkei Business Publications, Inc has reported that biogas measure­
ment is attracting attention as a non-invasive method that does not
burden the body [4]. Examples that have already been introduced
include the breath NO (nitric oxide) test for asthma and the urea breath
test for the helicobacter pylori test that is bad in the stomach and duo­
denum. Their usefulness is medically recognized. They introduced a
bio-sniffer (Tokyo Medical and Dental University) [5], a membrane-type
surface stress sensor (National Institute for Materials Science, Swiss
Federal Institute of Technology in Lausanne) [6], a breath sensor (Na­
tional Institute of Advanced Industrial Science and Technology, Figaro
Engineering Inc), a breath ammonia sensor (FUJITSU LABORATORIES
LTD.), A breath sensor (NTT DOCOMO, INC.) And a breath ammonia
sensor (NIHON DEMPA KOGYO CO., LTD., The University of Kita­
kyushu) as typical biogas sensors in Japan.
Various types of gas sensors and odor sensors have been developed.
Semiconductor-type gas sensors are highly reliable sensors that have
been used in gas alarms for many years. Various metal oxides have been
studied for gas sensors. SnO2, In2O3 and WO3 have advantages in sta­
bility among them. These materials are therefore used as commercial
sensors. SnO2 was the first material developed as a semiconductor
sensor. Research on various SnO2 structures, basic properties and ad­
ditives has been carried out for many years. Research has also been
conducted on the mechanism of SnO2 type sensors. SnO2 is one of the
most important materials for semiconductor sensors in terms of both
application and basic science. However, SnO2 thick film for gas alarms is
not sufficient to detect low-concentration biogas and odors. Therefore,
the development of SnO2 nanostructures has been attracting attention in
recent years in order to further improve the characteristics of SnO2 type
gas sensors.
In this review, semiconductor-type gas sensors are focused on
because they are highly stable and reliable and have many years of
commercial experience in areas such as gas leak detection [7–10]. In
particular, the use of SnO2 nanomaterials is highlighted because they are
being actively researched and developed as sensing elements for
semiconductor-type gas sensors. Moreover, examples of research and
development in this area over the past decade are presented.
The number of research papers has been investigated on the Web of
Science on 22 March, 2022 (Fig. 1). Key words of the chemical formula
of the sensor material and “gas sensor” are used for search. For instance,
the keywords of “SnO2” and “gas sensor” are used to search for SnO2 gas
sensors. The number of searched articles for n-type SnO2, ZnO, TiO2,
WO3, In2O3, Fe2O3, or CeO2 is 7516, 6952, 2978, 2402, 1600, 1100, or
396, respectively. The searched articles for p-type CuO, NiO, Co3O4,
Cr2O3, or Mn3O4 is 1202, 1110, 603, 187, or 37, respectively. The per­
centage of searched papers for n-type or p-type is 88.0% or 12.0%,
Fig. 1. Studies on n- and p-type oxide semiconductor gas sensors (internet
search of Web of Science on 22 March, 2022).
2
Sensors and Actuators: B. Chemical 364 (2022) 131876
respectively. The percentage of searched papers for SnO2, ZnO, TiO2,
WO3, In2O3, Fe2O3, or CeO2 is, 28.82%, 26.65%, 11.42%, 9.21%, 6.13%,
4.22%, or 1.52%, respectively. The percentage of searched papers for
CuO, NiO, Co3O4, Cr2O3, or Mn3O4 was 4.61%, 4.26%, 2.31%, 0.72%, or
0.14%, respectively. There are more papers on gas sensors using n-type
oxides than those on p-type. In particular, SnO2 has received a great deal
of attention. Gas sensors with SnO2 is focused on in this review. Espe­
cially, recent advances in SnO2 nanostructure based gas sensors are
reviewed.
2. Development of SnO2 nanostructures for gas sensing
Metal oxides, such as SnO2, ZnO, and TiO2, are used in various ap­
plications such as gas sensing, molecular sensing, and for fabricating
secondary batteries and catalysts. In particular, metal oxide nano­
materials are expected to exhibit outstanding device characteristics
owing to the effects of their high specific surface area and specific crystal
planes that exhibit unique physical properties, chemical characteristics,
crystal defects, surface defects, and quantum effects. The synthesis of
various SnO2 nanostructures has been attempted because SnO2 exhibits
excellent characteristics as a semiconductor-type gas sensor.
There are active reports on the sensor performance, sensing mech­
anism, guidelines for development, etc. for semiconductor gas sensors
using SnO2 [7–10]. N. Yamazoe and K. Shimanoe have reported valuable
guidelines for development of metal oxide nanostrures as follows [7].
Crystallite sizes of oxide semiconductors should be as small as possible.
Sensitizers should be dispersed as finely as possible. Sensing layer
thickness and porosity should also be optimized to improve selectivity
and durability.
In this review, SnO2 nanomaterials and detection limit of low-
concentration gas have been focused. Gas sensing mechanism of
semiconductor-type gas sensor is discussed in Section 2.1. Nano­
materials are categorized to 0D (nanoparticles), 1D (wires, needles,
whiskers, belts, etc.) or 2D (nanosheets). The 0D nanomaterials are
reviewed in Sections 2–2. The 1D nanomaterials are reviewed in Sec­
tions 2–3. 2D heterostructure is reviewed in Sections 2–4. 2D nanosheet
is discussed in detail in Section 3 because the 2D nanosheet is expected
to be developed further for low-concentration gas sensing.
2.1. Gas sensing mechanism of semiconductor-type gas sensor
Gas sensing mechanism of semiconductor-type gas sensor has been
discussed for both of n-type metal oxides [7] or p-type metal oxides [11].
Metal oxide particles in n-type semiconductor gas sensor act as receptors
and transducers. The role of a transducer is played by each contact be­
tween the particles. Interface between particles is the most resistant part
of the gas sensor. It determines the resistance of the gas sensor. The
surface space charge layer model or the double Schottky barrier model
are shown in Fig. 2a or Fig. 2b [7], respectively. The thickness of the
depletion layer (w) increases as oxygen adsorption as anionic species
(typically O− ) increases. It decreases as the adsorbed oxygen is
consumed with an inflammable gas such as H2. The double Schottky
barrier is formed across the contact between particles. Height of the
barrier changes to induce the contact resistance change and the resis­
tance change in the gas sensor (Fig. 2b) [7]. The receptor model in
Fig. 2a [7] assumes that the semiconductor particles are sufficiently
large. The mechanism has been further discussed in details to give
quantitative information regarding gas response. Size of the metal oxide
nanoparticles is very tiny (typically about 10 nm in diameter) in recent
advanced gas sensors. The space charge layer can easily extend over the
entire area of grains; that is, w grows to grain radius (r), at PO2 signif­
icantly below that in air, PO2 (Fig. 2c) [7]. A new process of electron
depletion has to take place afterward until the grains reach electrostatic
equilibrium with oxygen adsorption at PO2 (a). A mechanism is pro­
posed in which electron depletion is achieved by shifting the Fermi level
downward by pkT. Electrons move near surface of the particles as shown
Y. Masuda
Fig. 2. Diagrams of electron depletion for oxide grains and the resistance of contact between grains. (a) Space charge layer model, (b) double Schottky barrier model,
(c) regional and volume depletion model, (d) surface conductive grains contact model, (e) volume depletion model for the dendric growth of thin nanosheet.
in Fig. 2d [7].
Regional and volume depletion model [7] can be applied to the
nanosheets. Separated nanosheets have been synthesized with exfolia­
tion method [12–16]. Grain boundary is formed between each separated
nanosheets. On the other hand, a dendritic structured film of SnO2
nanosheet has been developed with facet controlled growth method
[17]. Dendritic growth governed the crystal growth of the SnO2 (101)
nanosheet assembled film. The branch angle of the connected nano­
sheets is in two types of connections, which are defined by the branch
angle of either 90◦ (type I) or 46.48◦ (type II).
Volume depletion model can be applied to the dendric growth of thin
nanosheet (Fig. 2e). The SnO2 nanosheets in the dendritic structure has a
thickness of 5–10 nm and an in-plane size of 100–1600 nm [17]. Half of
nanosheet thickness (t) is smaller than depletion layer thickness (w).
Electrons move without influence of grain boundary and Schottky bar­
rier. Conductance is influenced by electron concentration.
Half of the sheet thickness (t) in Fig. 2e is illustrated with the same
size as the grain radius (r) in Fig. 2c volume depletion and Fig. 2d. Both
of the nanoparticles with w=r (Fig. 2c, volume depletion) and the
dendric growth of thin nanosheet with w=t/2 (Fig. 2e) are the maximum
size to realize volume depletion model. The dendric-structured nano­
sheet film has effective conductive path compared with particulate film
having many grain boundaries. Therefore, the dendric-structured
nanosheet film has the advantage to form the ultra thin high response
membrane for a microelectromechanical system (MEMS)-type
microsensor.
Volume depletion model can be also applied to the grain boundary of
thin nanosheets. Separated thin nanosheets can be synthesized with the
solution process [17]. Electrons move without influence of grain
boundary and Schottky barrier as shown in volume depletion model for
nanoparticle in Fig. 2c-d. Conductance is influenced by electron
concentration.
On the other hand, an oxidizing gas such as NO2 increases the
resistance of the semiconductor gas sensor for the following reasons.
Similar to the case where oxygen is negatively charged on the surface of
an n-type oxide semiconductor such as SnO2 particles, when an
oxidizing gas such as NO2 is adsorbed on the surface of SnO2 particles,
electrons are trapped and NO2 becomes NO-2. Therefore, the gas sensor
shows a higher resistance value in the oxidizing gas than in the air.
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Sensors and Actuators: B. Chemical 364 (2022) 131876
2.1.1. Hierarchically structured SnO2 microspheres
[1-ppm-formaldehyde (HCHO)].
Li et al. developed SnO2 microspheres with a hierarchical structure
for formaldehyde (HCHO) gas sensing [18], which were synthesized
using a hydrothermal method without the use of polymer templates or
surfactants (Fig. 3a). The as-synthesized SnO2 microspheres were
composed of numerous small spheres with an average diameter of
approximately 250 nm. Each small sphere consisted of numerous pri­
mary nanocrystallites with an average size of approximately 8 nm
(Fig. 3b− c). The SnO2 microspheres exhibited gas sensing responses
(Ra/Rg) of 5.72, 7.70, 10.85, 21.12, 38.26, 66.25, and 144.90 for 1, 3, 5,
50, 100, 200, and 500 ppm formaldehyde, respectively, at an operating
temperature of 200 ◦ C. Additionally, the response to 100 ppm formal­
dehyde was higher than that of acetone (6.42), ammonia (1.74), xylene
(1.99), methanol (19.38), and toluene (1.55) (Fig. 3d). The ~8-nm-sized
nanocrystallites exhibited superior selectivity for formaldehyde gas
sensing. Moreover, the reaction mechanism of the SnO2-microspher­
e-based gas sensor for formaldehyde sensing was elucidated (Fig. 3e− f).
2.1.2. Single-atom Pt-functionalized 9-nm-thick SnO2 thin film
[10-ppb-triethylamine, LOD: 7 ppb].
Xu et al. fabricated single-atom Pt-functionalized SnO2 (Pt/SnO2)
thin films with thicknesses of 4–18 nm [19]. The 9-nm-thick Pt/SnO2
films showed an optimal response to 10 ppb triethylamine (TEA) owing
to their thickness being comparable to the Debye length. A decrease in
the film thickness to 4 nm led to a carrier concentration that was two
orders of magnitude lower. The LOD of the Pt/SnO2 sensor was esti­
mated to be 7 ppb. Additionally, the effects of the Pt catalyst and the
SnO2 thickness were discussed.
SnO2 thin films were deposited on SnO2/Si wafers by thermal atomic
layer deposition (ALD) for application as sensing layers in resistive gas
sensors. Tetrakis(dimethylamino)tin(IV) (TDMASn) and H2O were used
as the precursors. Single-atom Pt catalysts deposited on the 9-nm-thick
SnO2 film led to a considerable enhancement in the sensor response
and a decrease in its operating temperature. The response of Pt/SnO2 to
10 ppm TEA was as high as 136.2 at 200 ◦ C, which was almost seven
times higher than that of SnO2 at 260 ◦ C (20.3). The response time of the
Pt/SnO2 sensor was 3 s, which was only half that of SnO2. The Pt/SnO2
sensor recovered within 6 s, which was two orders of magnitude faster
than that of pure SnO2 (300 s). The extremely rapid response–recovery
Y. Masuda
dynamics of the Pt/SnO2 sensor were attributed to the Pt single atoms,
which reduced the activation energy of surface reactions and enhanced
the adsorption of TEA in the response stage and the desorption of the
resultant molecules during recovery [20]. The LODs of the Pt/SnO2 and
SnO2 sensors for TEA were calculated to be 7 ppb and 98 ppb, respec­
tively, which were lower than those of other sensing materials such as
4
Sensors and Actuators: B. Chemical 364 (2022) 131876
Fig. 3. (a) A schematic illustration of the for­
mation process of SnO2 microsphere. (b)
HRTEM image of as-synthesized SnO2 micro­
spheres and (c) the corresponding HRTEM
image with obvious SnO2 lattice fringe. (d)
Response of the SnO2 microspheres gas sensor
to 100 ppm of different gases at 200 ◦ C. A
schematic diagram of the proposed reaction
mechanism of the SnO2 microspheres gas sensor
to formaldehyde: (e) in air, (f) in formaldehyde
(HCHO) [18].
Reprinted with permission from ref. [18]
Copyright 2021 Elsevier. .
WO3/SnO2 nanoparticles (LOD: 1 ppm) [21], NiO/SnO2 hollow spheres
(2 ppm) [22], SnO2 hollow microfibers (2 ppm) [23], TiO2/SnO2
nanosheets (2 ppm) [24], Zn2SnO4/SnO2 microspheres (500 ppb) [25],
MoS2/SnO2 nanofibers (5 ppm) [26], Au/Mg-TiO2/SnO2 nanosheets
(2 ppm) [27], Pd/In2O3 microstructures (1 ppm) [28], Al2O3/α-Fe2O3
nanofibers (500 ppb) [29], Au/ZnO nanorods (1 ppm) [30],
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Co3O4/In2O3 microtubes (2 ppm) [31], α-MoO3 nanoflowers (500 ppb)
[32], Au/SnO2/α-Fe2O3 nanoneedles (2 ppm) [33], ZnCo2O4
single-layer nanochain (5 ppm) [34], Au-TiO2/m-CN nanocomposite
(1 ppm) [35], Au/α-Fe2O3 nanorods (1 ppm) [36], In2O3 microtubes
(100 ppb) [37] and Au/Co3O4/W18O49 hollow spheres (81 ppb) [38]
(Table 1). To characterize the sensor selectivity, the thin-film sensors
were further exposed to a group of molecules including C6H15N, C2H6O,
CH3COCH3, CH3(CH2)3OH, CH3OH, HCHO, and C7H8. The Pt/SnO2
sensor showed improved responses to all the gases. The selectivity co­
efficients calculated using the responses to the various analytes indi­
cated that the single-atom Pt catalysts dramatically improved the
selectivity for TEA. These investigations revealed that the outstanding
sensing performance originated from the synergistic combination of the
optimized film thickness, which was comparable to the Debye length of
SnO2, the spillover activation of oxygen by the single-atom Pt catalysts,
and the OVs in the SnO2 films. The Debye length, LD, is a characteristic of
a semiconductor material for a particular donor concentration and can
be calculated as follows: [39].
( / )1/2
LD = ε0 εkB T q2 nc , 450 ◦ C for 12 h using a microheater under a flow of synthetic air. The
where kB is the Boltzmann’s constant, ε is the dielectric constant, ε0 is
the permittivity of free space, T is the operating temperature, q is the
electron charge, and nc is the carrier concentration, which corresponds
to the donor concentration assuming full ionization. The carrier con­
centration was obtained from Hall measurements. The temperature,
carrier concentration, mobility, and Debye length of the 4-nm-thick
SnO2 film were 300 K, 2.17 × 1020 m− 3, 121.30 cm2/V⋅s, and
375.1 nm, respectively. whereas those of the 9-nm-thick SnO2 film were
300 K, 9.22 × 1022 m− 3, 34.3 cm2/V⋅s, and 14.5 nm, respectively. The
carrier concentration of the 9-nm-thick SnO2 film was higher than that
of the 4-nm-thick counterpart, whereas the mobility and Debye length of
the 9-nm-thick SnO2 film were lower than those of the 4-nm-thick
equivalent.
Additionally, the sensing properties of the Pt/SnO2 devices were
compared with those of commercial TGS 2602 gas sensors (Figaro En­
gineering Inc.). The TGS 2602 gas sensor had a thick-film sensing ma­
terial for VOC detection. The sensing layers of the three devices were
found to exhibit inhomogeneous surfaces, along with certain cracks in
the sensing layers, which possibly led to unsatisfactory reproducibility
of the commercial sensors. Moreover, gas sensing tests confirmed that
the three commercial devices delivered remarkably different sensing
responses to TEA at an optimal operating temperature of 260 ◦ C. The
TGS 2602 gas sensors had a response (Ra/Rg) of 15–16 for 10 ppm TEA,
whereas those of the Pt/SnO2 and SnO2 sensors were 136.2 and 20.3,
respectively.
2.1.3. Pulse-driven gas sensor containing Pd-loaded SnO2 nanoparticles
[1-ppb-toluene, LOD: 200 ppt or 7 ppt].
Suematsu et al. developed a heater-switching pulse-driven micro gas
sensor[40] (Fig. 4a–b) composed of a microheater and a sensing elec­
trode fabricated with Pd-loaded SnO2 clustered nanoparticles (CNPs).
The Pd-SnO2 nanoparticles were used in the sensor because of their high
sensitivity to toluene gas[41]. A SnCl4.5 H2O solution (1 M) was added
to a NH4HCO3 solution (1 M) to form stannic acid gel (SnO2⋅nH2O), to
which Pd[(NO2)2(NH3)2] was subsequently added. NH3 solution was
used to control the pH of the solution in the 9.3–10.6 range. The solution
was hydrothermally treated at 200 ◦ C for 3 h at 10 MPa with stirring at
600 rpm. This reaction was controlled by introducing nitrogen into the
reactor. Micro droplets of a paste containing the Pd-SnO2 nanoparticles
and glycerin at a 1:1 ratio (w/w) were placed onto a MEMS-type
microsensor using a capillary tube and a micromanipulation system
(PatchMan NP2, Eppendorf) (Fig. 4c–e). The sensor was sintered at
sensor was heated in pulse-heating mode, and the heater was repeatedly
switched on and off. The volatile organic compound (VOC) gas perme­
ated through the particulate film when the sensor was not heated
(Fig. 4a–b). In contrast, the gas expanded when the heater was switched
on, and a portion of it was exhausted. The sensor response (Ra/Rg)
calculated using the initial electrical resistance was 3 and 4.5 for 1 ppm
and 8 ppb toluene, respectively (Fig. 4f− g). Moreover, the
sensor-response-related detection limit of the pulse-driven sensor con­
taining the Pd-SnO2 nanoparticles was calculated to be approximately
200 ppt toluene.
Suematsu et al. also fabricated Pd-SnO2 CNPs on a microsensor de­
vice with a double-pulse-driven mode [42]. This mode assisted in
switching the heater-on periods during the high-temperature preheating
and measurement phases and the rest phase during the heater-off period
between the preheating and measurement phases. The electrical resis­
tance in synthetic air and the sensor response to toluene increased with
increasing preheating temperature because of an increase in the amount
of O2− adsorbed on the particle surfaces. The sensor response was
improved by extending the interval between the preheating and mea­
surement phases. Moreover, the lower detection limit for toluene gas
was improved to 7 ppt using preheating and measurement temperatures
of 400 ◦ C and 250 ◦ C, respectively, and a rest time of 100 s

Table 1
Comparison of TEA detection performances of various materials [19], [21–38].
Sensing materials Operating temperature (℃) Response/ppm Response/recovery time (s) LOD (ppm) Reference

WO3/SnO2 nanoparticles 220 87/50 6/7 1 [21]

NiO/SnO2 hollow spheres 220 46.5/10 11/34 2 [22]
SnO2 hollow microfibers 270 49.5/100 14/12 2 [23]
TiO2/SnO2 nanosheets 260 52.3/100 12/22 2 [24]
Zn2SnO4/SnO2 microspheres 250 19.6/20 2/184 0.5 [25]
MoS2/SnO2 nanofibers 230 106.3/200 – 5 [26]
Au/Mg-TiO2/SnO2 nanosheets 260 30.43/50 9/95 2 [27]
Pd/In2O3 microstructures 220 47.56/50 4/17 1 [28]
Al2O3/α-Fe2O3 nanofibers 250 15.19/100 1/17 0.5 [29]
Au/ZnO nanorods 40 22/50 11/15 1 [30]
Co3O4/In2O3 microtubes 250 786.8/50 47/20 2 [31]
α-MoO3 nanoflowers 250 416/100 3/1283 0.5 [32]
Au/SnO2/α-Fe2O3 nanoneedles 300 39/100 4/203 2 [33]
ZnCo2O4 singlelayer nanochain 200 13/100 7/57 5 [34]
Au-TiO2/m-CN nanocomposite 175 78.9/50 – 1 [35]
Au/α-Fe2O3 nanorods 40 17.5/50 12/8 1 [36]
In2O3 microtubes 300 72/100 12/650 0.1 [37]
Au/Co3O4/W18O49 hollow spheres 270 283.1/50 9/14 0.08 [38]
Pt/SnO2 film (9 nm, ALD) 200 136.2/10 3/6 0.01 [19]
SnO2 film (9 nm, ALD) 260 20.3/10 6/300 0.1 [19]

5
Y. Masuda
2.1.4. SnO2 1D nanostructures
Prof. Sheikh Akbar developed SnO2 nanowires [43,44], hierarchical
SnO2 nanowire–TiO2 nanorod brushes on fluorine doped tin oxide (FTO)
substrates [45], core–shell TiO2–Al2O3 nanowires [46,47]. The n-type
SnO2 nanowires were coated by magnetron sputtering and chemical
vapor deposition with n-type TiO2, WO3, ZnO, Nb2O5, and MoO3 as well
as p-type Cr2O3, Co3O4 and NiO [48]. He reviewed 1D nanostructured
metal oxide gas sensors based on SnO2, ZnO, TiO2, In2O3, WOx, AgVO3,
CdO, MoO3, CuO, TeO2 and Fe2O3 [49]. He also reported on role of
oxygen vacancies [50], metal oxide heterojunctions [51–53] and gas
selectivity mechanisms [54] using examples of SnO2 nanofibers [55],
Co3O4 nanofibers [56], Co3O4 modified SnO2 nanofibers [57], NiO/ZnO
sheets/flowers [58], NiO/ZnO hollow microspheres [59], Co3O4 nano
rhombus [60], Co3O4 sea urchins [61], Co3O4 nanocubes [62], Co3O4
nanosheets [63], Co3O4 nanorods [63], Co3O4 nanocubes [63], and
Co3O4 powders [63]. He discussed gas selectivity of various p-n heter­
ojunctions, n-n heterojunctions and p-p heterojunctions. It was
concluded that the process to design selective sensors involved the type
of oxides, the ratio of oxides, and the morphology. Various oxide com­
binations may then be incorporated into a sensor array to identify gas
using machine learning [64].
2.1.5. SnO2 nanowires with a surface amorphous layer
[100-ppm-ethanol].
6
Sensors and Actuators: B. Chemical 364 (2022) 131876
Fig. 4. Schematic illustrations of gas-diffusion behavior in
the (a) heating-off and (b) heating-on phases. (c) Photo­
graphic and (d) SEM images of a blank MEMS sensor. (e)
Side view of the SnO2 microsensor. (Third step) (f) Tran­
sient response curve of the Pd-SnO2 clustered nanoparticle
(CNP) microsensor to various toluene concentrations at
1.04 V (~250 ◦ C). (g) Relationship between the response
of the Pd-SnO2 CNP sensor and toluene concentration [40].
Reprinted with permission from ref. [40] Copyright 2021
American Chemical Society.
Pan et al. prepared SnO2 nanowires by chemical vapor deposition
(CVD) [65] (Fig. 5a–b). The SnO2 nanowires were modified by Ar/O2
plasma treatment through preferential etching of lattice oxygen atoms
(Fig. 5c). The plasma treatment gradually modified the chemical
composition and morphology of the SnO2 nanowires. The
plasma-treated SnO2 nanowires showed a higher conductance than that
of the as-deposited SnO2 nanowires. This was due to the effect of band
bending induced by surface charges associated with the additional states
resulting from the shallow donor states of the abundant oxygen va­
cancies (OVs). X-ray photoelectron spectroscopy (XPS) profiles of the
as-deposited and plasma-treated SnO2 nanowires (synthesized at 40 W)
showed a distinct shift in the Sn 3d peaks toward a lower binding energy,
indicating chemical reduction of the Sn species upon exposure to radi­
ofrequency plasma. The TEM micrograph of the nanowires showed 1D
heterostructures with a crystalline SnO2 core and an amorphous over­
layer, and corroborated the anticipated structural changes by ions with a
higher kinetic energy that impinged on the nanowire surface. The rough
amorphous overlayer in the plasma-treated samples increased the den­
sity of dangling bonds and free lattice sites, thereby favoring surface
adsorption phenomena. The plasma-treated SnO2 nanowires (40 W) had
a gas sensing response (Ra/Rg, where Ra: resistance of the sensor in air,
and Rg: resistance of the sensor in the target gas) of 4.98 for 100 ppm
ethanol at 250 ◦ C, which was higher than that of the as-deposited SnO2
nanowires (1.69). The plasma treatment was effective in increasing the
Y. Masuda
Fig. 5. (a) SEM micrograph of as-deposited SnO2 nanowires. HR-TEM images of
(b) as-deposited and (c) plasma-treated (40 W) SnO2 nanowires [65].
Reprinted with permission from ref. [65] Copyright 2021 American Chemi­
cal Society.
sensor response, and was primarily caused by the amorphous surface
layers with nonstoichiometric surface compositions. Moreover, the high
volume of dangling bonds and free lattice sites in the amorphous surface
layers improved the surface adsorption phenomenon.
2.1.6. SnO2 nanorod particles with {110} facet
[44-ppm-ethanol].
Kuang et al. synthesized hierarchical SnO2 nanostructures made of
superfine nanorods using a hydrothermal method for ethanol sensing
[66] (Fig. 6). The hierarchical SnO2 sensor (S3) was prepared by first
dissolving zinc acetate (Zn(CH3COO)2; 0.05 g) in a mixture of deionized
(DI) water (15 mL) and ethanol (15 mL) with stirring. NaOH (0.9 g) and
stannic chloride pentahydrate (SnCl4.5 H2O) (1 mmol) were succes­
sively dissolved in the preceding mixture. The resulting solution was
maintained at 180 ◦ C for 24 h, and the subsequently obtained powder
was dissolved in ethanol to form a paste, which was coated onto an
Al2O3 tube to form an ~100–200-μm-thick film between two parallel Au
electrodes. The SnO2 film was sintered at 400 ◦ C for 2 h in air, and the
fabricated gas sensor was aged at 240 ◦ C for 72 h to improve the stability
and repeatability. The S3 sensor showed a response (Ra/Rg) of 44 for
50 ppm ethanol at a heater current of 150 mA. In addition, the synthesis
protocol was comprehensively explained. Nucleation was found to be
7
Sensors and Actuators: B. Chemical 364 (2022) 131876
initiated by the decomposition of the preformed ZnSn(OH)6 induced by
alkali etching. The diameter and density of the nanorods were controlled
by the addition of NaOH, which yielded smaller and denser nanorods.
Moreover, nucleation was facilitated by NaOH, leading to rapid growth
in all directions.
2.1.7. Oriented SnO2 nanorod array
[200-ppb-NO2, LOD: 132 ppt].
Song et al. fabricated SnO2 nanorods for the detection of 200 ppb
NO2 at a relative humidity (RH) of 20% and estimated a detection limit
of 132.3 ppt [67]. Ion-activated sensing, in which ionic conduction was
realized by the adsorbed hydroxide layer in the presence of humidity,
was established, which led to proton transport [68,69].
A 1-µm/550-µm-thick SiO2/Si substrate with 150-nm/30-nm-thick
Pt/Ti interdigitated electrodes was used as the sensor. The substrate
had 20 electrodes in a 1 mm × 1 mm area, which were spaced apart by
5 µm. The SnO2 nanorods were deposited on the substrate by glancing
angle deposition (GAD) using an electron beam evaporator (Fig. 7a− b).
The samples were annealed at 550 ◦ C for 2 h under a gas flow rate of
1000 sccm. The sensor resistance was measured using a DC bias voltage
of 0.5 V. The sensor showed a linear response (Rg/Ra ~ 1) in the range of
200 ppb to 10 ppm at 20% RH (Fig. 7c− d). However, the response
saturated for NO2 concentrations above 10 ppm because the active sites
were almost covered by the NO2 species. The theoretical detection limit
(signal-to-noise ratio > 3) was calculated to be 132.3 ppt NO2 under
20% RH. The gas selectivity of the SnO2 nanorods was measured under
dry and 20% RH conditions using 5 ppm NO2; 10 ppm CO, C2H5OH, and
C7H8; and 1000 ppm H2 at an applied voltage of 0.5 V. The highest
response and selectivity to NO2 were observed at 20% RH (Fig. 7e)
compared to the other tested gases because the reducing gases could not
react with the hydroxide layer. Moreover, the sensing mechanism under
high-humidity conditions was explored (Fig. 7g–j). Humidity is known
to degrade gas sensing properties, such as response, response time, and
recovery time, which is referred to as water poisoning [70]. However,
the response of the SnO2 nanorods improved with increasing RH from
0% to 20% and decreased with a further increase in RH to 80%.
Essentially, the SnO2 nanorods exhibited improved sensing properties
under humid conditions and exhibited an excellent response at 20% RH
compared to that under dry conditions only at room temperature.
Therefore, the conventional electron exchange reaction was presumed
to occur above 100 ◦ C, and the ion-activated mechanism was operative
at room temperature. In addition, sensors were fabricated using NiO,
Cr2O3, Co3O4, and WO3 nanorods for the detection of 5 ppm NO2 at
0.5 V under 20% RH (Fig. 7f). The sensing resistances of the Cr2O3,
Co3O4, and WO3 nanorods were not significantly altered upon exposure
to NO2; however, only the SnO2 nanorods exhibited enhanced sensing
performance.
2.1.8. SnOx nanopillars
[10-ppt-H2 in vacuum].
D’Arsié et al. fabricated SnOx nanopillars and evaluated their sensing
performance in an ultra-high-vacuum (UHV, 10− 10 mbar) chamber for
10 ppt H2 at 230 ◦ C [71]. This contributed to the detection of low
concentrations of H2 using SnOx nanopillars, although the UHV exper­
iments did not replicate the typical operational conditions of the sensor.
To prepare the SnOx nanopillars, ITO/glass substrates were first
sequentially exposed to H2 and C2H2 at ~650 ◦ C to form vertical
nanostructures of carbon filled with tin [72]. These specimens were
heated at ~650 ◦ C in oxygen to incinerate the carbon shells. No further
changes in the structures were observed at this temperature upon
incineration of the carbon. The final sensor was composed of a glass
support coated with an ~120-nm-thick Sn-depleted ITO film covered
with vertical nanopillars of SnOx (Fig. 8a− b).
The sensor showed variation in resistance (R − R0)/R0 [%]) for H2,
CH4, and O2 detection at room temperature and at 90 ◦ C, where R is the
resistance after 100 s of gas exposure and R0 is the initial resistance prior
Y. Masuda
Fig. 6. (a) Schematic for the possible growth of the hierarchical SnO2 nanostructures made of superfine nanorods. FESEM (b), TEM (c) and HRTEM (d) images of the
hierarchical SnO2 nanostructure made of superfine nanorods (S3) [66].
Reprinted with permission from ref [66]. Copyright 2021 Elsevier.
to the introduction of the gas in the experimental chamber (Fig. 8c). The
experiment was performed under low-vacuum conditions (10− 5 mbar
base pressure) at 90 ◦ C and 10 ppm. The sensor exhibited variation in
resistivity (15–20%) for H2 and O2, and showed a one-order-of-
magnitude lower sensitivity for CH4. The sensor was insensitive to
CO2 and N2 concentrations of up to 1000 ppm. Moreover, the SnOx
nanopillar sensor responded to 10, 50, 100, and 500 ppt H2 at 230 ◦ C in
UHV (Fig. 8d). However, the sensor did not respond to ppt-level con­
centrations of CH4, CO2, CO, NO2, and N2 at 230 ◦ C. This behavior can
be explained by the effects of the gas molecules interacting with n-type
SnOx nanopillars [73,74]. Negative charges trapped by oxidizing species
generally cause upward band bending, whereas the reaction with
reducing gases, such as H2, causes downward band bending. However, it
is worth noting that competitive adsorption and replacement of the
adsorbed molecules could decrease or even reverse the band bending,
resulting in an opposite variation in the conductivity [73,74]. In addi­
tion, the sensing properties of the SnOx nanopillars were compared with
those of a commercial sensor for VOCs, NH3, and H2S (Figaro Engi­
neering Inc., TGS 2602 [75]). Both sensors exhibited similar responses
for NH3; however, the SnOx nanopillars showed high response and re­
covery rates compared with those of the commercial sensor for 2.2, 3.6,
and 30 ppm NH3 (Fig. 8e− h). Furthermore, the authors comprehen­
sively elucidated the energy band alignment at the ITO/SnO2 isotype
heterojunction [76] and the electron injection from the SnO2 nanopillars
to the substrate upon exposure to a reducing gas (Fig. 8i − j).
2.1.9. Y-doped SnO2 nanofibers
[20-ppb-NO2, LOD: 103.71 ppt].
Kim et al. developed Y-doped SnO2 nanofibers [77] containing OVs
and hydrophobic Y2O3 nanoparticles on their surfaces for sensing 20 ppb
NO2, and estimated an LOD of 103.71 ppt under humid conditions.
To synthesize the nanofibers, a viscous solution of pure SnO2 nano­
fibers was first prepared by dissolving 0.5 g of tin(II) chloride dihydrate
8
Sensors and Actuators: B. Chemical 364 (2022) 131876
(SnCl2.2 H2O) and 1.0 g of polyvinylpyrrolidone (PVP, molecular
weight = 1,300,000) in N,N-dimethylformamide (DMF; 0.425 mL) and
ethanol (0.425 mL), and stirring the mixture for 12 h at room temper­
ature (Fig. 9a). A solution of the Y-doped SnO2 nanofibers was synthe­
sized by replacing tin(II) chloride dihydrate with an equal amount of
yttrium(III) nitrate hexahydrate (Y(NO3)3.6 H2O) in the aforementioned
protocol. The nanofibers were obtained by electrospinning from a
mixture of the two aforementioned solutions at 10.0 kV between the
sample collector and the syringe pump. The nanofibers were collected
on SiO2/Si substrates and subsequently calcined in air at 550 ◦ C for 1 h
to obtain the Y-doped SnO2 nanofibers (Fig. 9b–d).
The sensor with 1 at% Y-doped SnO2 nanofibers exhibited high sta­
bility for NO2 sensing in the RH range of 0–87% (Fig. 9e− k). The re­
sponses (Ra/Rg or Rg/Ra) of the 1 at% and 5 at% Y-doped SnO2
nanofibers to 10 ppm NO2 at 200 ◦ C under dry conditions were 70.38
and 11.06, respectively, and those under 87% RH were 97.94 and 12.17,
respectively; the changes in response (ΔS) were calculated to be 0.39
{(97.94 − 70.38)/70.38} and 0.1 {(12.17 − 11.06)/11.06}, respec­
tively. The Y-doped SnO2 nanofibers exhibited superior responses and
smaller changes in the response compared to those of other materials
such as ZnO thin films [78]，WS2/graphene aerogel [79], Al-doped ZnO
[80], Cr2WO6 [81], Rb2CO3-decorated In2O3 [82], and Rb-doped In2O3
[83] (Table 2). The response curves of pristine and 1 at% Y-doped SnO2
nanofibers as a function of NO2 concentration were used to estimate the
sensor sensitivity and LOD, which were calculated for signal-to-noise
ratios of over three. The LOD of the sensor with the 1 at% Y-doped
SnO2 nanofibers was estimated to be 103.71 ppt NO2, which was nearly
six times higher than that of the pristine SnO2 sensor.
Furthermore, the mechanism behind the highly stable sensor oper­
ation under humidity was elucidated based on experimental results and
van-der-Waals (vdW)-corrected DFT calculations (Fig. 9l− q). Surface
OVs were created by aliovalent doping of Y atoms into the SnO2 nano­
fibers. These vacancies made the sensor surface energetically more
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 7. (a) Schematic illustration of sensor fabrication by glancing angle deposition via electron beam evaporation. (b) Planar and cross-sectional SEM images of the
SnO2 nanorods. (c) Response curves of the nanorods to 5 ppm NO2 as a function of RH at room temperature. (d) Response of the SnO2 thin film and nanorods upon
exposure to 5 ppm NO2. (e) Response of the SnO2 nanorods to different target gases at 20% RH. (f) Response to various metal-oxide-based nanorods. Schematic
illustrations of the sensor response to NO2 on (g) oxygen-adsorbed and (h) hydroxide-functionalized SnO2 surfaces. (i) Energy band structure at the surface of SnO2
featuring surface adsorbate levels of O2, OH, and NO2. The energy level ordering of the adsorbate levels follows the free-space electron affinity trends of the
respective molecules. (j) Schematics of highly ordered SnO2 nanorods and the double Schottky barrier model.
Reprinted with permission from ref. [67] Copyright 2021 John Wiley and Sons.

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 8. SEM images of vertical nanostructured

SnOx pillars on an ~150-nm-thick ITO/Sn-reduced
substrate acquired at tilt angles of (a) 45◦ and (b)
0 ◦ . The two images share the same scale bar;
moreover, they were obtained prior to the sensing
experiments and are representative of the post-
sensing morphology, as no changes could be
determined via SEM. (c) Response of the vertical
nanostructured SnOx pillars after exposure to
several gases at low temperatures (30 ◦ C or 90 ◦ C)
in low vacuum (10− 5 mbar) for 100 s (d) Response
of the SnOx nanopillar sensor to low-pressure H2
(corresponding to ppt amounts) at 230 ◦ C in UHV.
(Second step) (e) Variation in resistivities of the
vertical SnOx nanopillar sensor (blue profile) and a
commercial FIGARO sensor (Figaro Engineering
Inc., TGS 2602; dashed red line) after exposure to
30 ppm NH3 in air at room temperature. The NH3
exposure period is marked with a green back­
ground. The recovery times were fitted with double
exponential functions (dashed black lines). (f)
Observed fluctuations compared with (g) the signal
noise. (h) Variation in the resistivities of the verti­
cal SnOx nanopillar sensor (blue profile) and the
FIGARO sensor (red profile) after exposure to
3.6 ppm and 2.2 ppm NH3 (pulse in the millisecond
range). (i) Energy band alignment at the ITO/SnO2
isotype heterojunction. (j) Schematic of electron
injection from the SnO2 nanopillars to the substrate
upon exposure to a reducing gas. The junctions are
present only at the nanopillar/ITO interface.
Therefore, the current from source to drain does
not have to pass through any junction [71]. (For
interpretation of the references to color in this
figure legend, the reader is referred to the web
version of this article.)
(i) (adapted from a previous report [76]). (j)
Reprinted with permission from ref [71]. Copyright
2021 Springer Nature.

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

(caption on next page)

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 9. (a) Schematic illustration of the fabricated gas sensor and the concept of this work demonstrating the synergistic effect of oxygen vacancy and hydrophobic
Y2O3 in the Y-doped SnO2 nanofibers for selective NO2 adsorption in the presence of water vapor. (b) SEM images of the 1 at% Y-doped SnO2 nanofibers. (c) TEM
image of the 1 at% Y-doped SnO2 nanofiber. (d) Magnified TEM image of the 1 at% Y-doped SnO2 nanofiber. (Third step) Dynamic resistance curves of (e) pristine
SnO2 nanofibers, (f) the 0.5 at% Y-doped SnO2 nanofibers (Y0.5-SnO2), (g) the 1 at% Y-doped SnO2 nanofibers (Y1-SnO2), (h) the 5 at% Y-doped SnO2 nanofibers
(Y5-SnO2) to 10 ppm NO2 at 200 ◦ C in dry and humid conditions (RH = 0%, 17%, 52% and 82%). Resistance value of each sample in (i) air and (j) analyte gas as a
function of RH. (k) The ΔS value of the pristine and Y-doped sensors. (Fourth step) Optimized (110) slab structures of (l) pristine and (m) Y-doped SnO2. Blue-dotted
circles indicate the positions of two VO defects. Optimized (110) slab structures for NO2 adsorption in (n) pristine and (o) Y-doped SnO2. Optimized (110) slab
structures for H2O adsorption in (p) pristine and (q) Y-doped SnO2 [77].
Reprinted with permission from ref [77] Copyright 2021 Elsevier.

Table 2
Comparison of previously reported humidity-independent NO2 detection data [77], [78–83]. Reprinted with permission from ref [77]. Copyright 2021 Elsevier.
Sensing Materials Temp. (℃) NO2 conc. (ppm) Response (Ra/Rg or Rg/Ra) Response changes (ΔS) Reference

dry wet

ZnO thin film 450 200 94 70 (RH 10%) -0.26 [78]

WS2/graphene aerogel 180 2 ~3.3 ~3.0 (RH 60%) -0.09 [79]
Al-doped ZnO 300 5 ~8 ~2.4 (RH 40%) -0.7 [80]
Cr2WO6 200 2 ~8 ~11 (RH 20%) 0.38 [81]
Rb2CO3-decorated In2O3 RT 0.25 ~65 ~140 (RH 62%) 1.16 [82]
Rb-doped In2O3 75 5 1502 660 (RH 94%) -0.56 [83]
1 at% Y-doped SnO2 nanofibers 200 10 70.38 97.94 (RH 87%) 0.39 [77]
5 at% Y-doped SnO2 nanofibers 200 10 11.06 12.17 (RH 87%) 0.1 [77]

favorable for reacting with (and thereby detecting) NO2 molecules than
with water vapor. Moreover, the yttrium atoms that were not substituted
into the SnO2 lattice formed hydrophobic Y2O3 nanoparticles over the
entire surface of the nanofibers, which acted as synergistic co-agents for
repelling water vapor. The water contact angles of the pristine SnO2
nanofibers and the 0.5, 1, 3, 5, and 10 at% Y-doped SnO2 nanofibers
were estimated to be 80.4◦ and 94.5◦ , 107.8◦ , 121.7◦ , 144.7◦ , and
161.6◦ , respectively; essentially, the angle increased with increasing
concentration of Y. The authors concluded that hydrophobicity could be
exploited for detecting more target gases without interference from
water molecules, enabling the sensor to preserve its intrinsic sensing
ability with improved gas responses, even at high humidity levels.
2.1.10. SnO2 nanowires
[50-ppb-Cl2, LOD: 48 ppt].
Van Dang et al. fabricated SnO2 nanowires for detecting 50 ppb Cl2 at
50 ◦ C with an LOD of 48 ppt. SnO2, ZnO, and WO3 nanowires were
synthesized by CVD, as described henceforth [84].
A sensor chip with a microheater and a pair of Pt/Cr electrodes [85]
(Fig. 10a− b) was placed 3 cm away from a Sn-powder-containing quartz
tube. The sensor chip had arrays of catalytic Au islands and SnO2 or ZnO
nanowires to precisely grow nanowires in predefined areas; catalytic W
islands were used for fabricating WO3 nanowires. The catalytic islands
had an average diameter of 5 µm and were periodically arranged be­
tween the two Pt electrodes. The distance between the catalytic islands
was 5 µm. The samples were heated at 750 ◦ C for 30 min to grow the
SnO2 nanowires, with vacuum being maintained in the quartz tube
(~10− 1 Torr) by flowing a mixture of Ar (30 sccm) and O2 (0.5 sccm)
during the nanowire growth [86]. The nanowires grew only on the
predefined areas where the catalytic islands were deposited (Fig. 10c),
forming nanowire–nanowire junctions between the Pt/Cr electrodes
that acted as the sensing element. The SnO2 nanowires were 80 nm in
diameter and a few micrometers in length, and had homogeneous
morphology [86]. The morphologies and sizes of the ZnO and SnO2
nanowires were not significantly different. The Au-catalyst-assisted
growth of the ZnO and SnO2 nanowires followed the vapor­
–liquid–solid mechanism, in which the Au islands had identical thick­
nesses, which produced nanowires with similar diameters [87]. The
HRTEM image of a SnO2 nanowire (inset of Fig. 10c) showed clear lat­
tice fringes with an interspace of 0.26 nm, which corresponded to the
distance between the (101) planes of tetragonal SnO2, indicating that
the growth direction was 〈101〉 [88]. The ZnO nanowires were 80 nm in
diameter, a few micrometers in length, and exhibited homogeneous
morphology [85]. The HRTEM image showed the single-crystalline na­
ture of the ZnO nanowire. The interspacing between the two crystal
planes was 0.52 nm, indicating that the preferred growth direction was
the 〈0001〉 axis [89]. The WO3 nanowires were 350 nm in diameter,
several micrometers in length, and exhibited a rough morphology with a
nonhomogeneous diameter in which the bottom was larger than the top.
In addition, the WO3 nanowires were polygonal rather than circular, as
evidenced by their vapor–solid growth model, in which the vapor of the
source materials was transported to low-temperature zones and
condensed to form small crystal clusters, which were seeded into the
nanowires [90]. The HRTEM image also demonstrated that WO3 pre­
sented single crystallinity with an interspace of 0.38 nm, corresponding
to the (002) planes of the monoclinic structure; thus, the growth di­
rection was determined to be the 〈001〉 axis [91]. The gas response was
defined as S = RCl2/Rair, where RCl2 and Rair are the resistances of the
sensor in Cl2 and dry air, respectively. The SnO2 nanowires exhibited
higher sensitivity to Cl2 gas than that of the ZnO and WO3 nanowires
(Fig. 10b). Moreover, the SnO2 nanowire sensor showed superior
sensitivity at 50 ◦ C compared with that in the 100–300 ◦ C range
(Fig. 10d− e). The response (RCl2/Rair) of the SnO2 nanowire sensor to 50
ppb Cl2 at 50 ◦ C was approximately 57 (Fig. 10e). Additionally, the Cl2
gas detection limit of the SnO2 nanowire sensor was calculated to be 48
ppt at 50 ◦ C (Fig. 10g− h). The sensing mechanism of the SnO2 nanowire
sensor was believed to involve direct adsorption of a Cl2 molecule on the
metal oxide surface and its subsequent substitution with pre-adsorbed
oxygen, followed by lattice oxygen.
The SnO2 nanowires show a superior response to Cl2 gas compared to
that of other materials such as Pd-doped NiFe2O4 nanocrystals [92],
Sb-doped SnO2 nanoparticles [93], In2O3 thin film [94],
Fe2O3-modified ZnO thick film [95], MgO–In2O3 thin film [96], meso­
porous SnO2 [97], Te nanotubes [98], sulfonated copper phthalocyanine
films [99], zinc phthalocyanine nanobelts [100], and nanowires of
copper phthalocyanine [101] (Table 3). Moreover, the Cl2 response of
the SnO2 nanowire sensor is comparable to that of other mixed oxide
materials, such as CdIn2O4 powder [102], hydrothermally prepared
CdSnO3 [103], and CdSnO3 thick film [104]. The superior Cl2 response
of SnO2 than that of ZnO and WO3 was not clarified; however, this may
be related to the influence of defect levels in the sensing materials. Ahn
et al. [105] suggested that the abundant OVs in the ZnO nanowires
resulted in a superior response to the oxidizing gas. The OV-related peak
in SnO2 was the strongest and broadest in the photoluminescence

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 10. (a) Design of a nanowire-based sensor chip. (b) Responses of ZnO, SnO2, and WO3 nanowires to Cl2 gas. (c) SEM image of SnO2 nanowires; inset shows a
corresponding HRTEM image, with the arrow indicating the direction of growth of the nanowires. Sensing characteristics at ppb-level concentrations of Cl2: (d)
Transient resistance of the SnO2 nanowire sensor upon exposure to different concentrations of Cl2 (50–400 ppb) at various temperatures (50–300 ◦ C); (e) sensor
response as a function of Cl2 concentration measured at the investigated temperatures; and (f) selectivity of the sensor to different gases (CO, H2S, ethanol, and NH3)
measured at 400 ◦ C. (g) A fifth-order polynomial fit of ten baseline data points and the (h) linear fit of the response versus Cl2 gas concentration [84].
Reprinted with permission from ref. [84] Copyright 2021 American Chemical Society.

spectra of the SnO2, WO3, and ZnO nanowires. Van Dang et al. indicated
that OVs could be responsible for the superior response of the SnO2
nanowires to Cl2 compared to that of the ZnO or WO3 nanowires [84].
2.1.11. SnOx/SnS heterostructures
[1-ppb-NO2, LOD: 5 ppt].
Tang et al. demonstrated the detection of 1 ppb NO2 using SnOx/SnS
heterostructures and obtained an LOD of 5 ppt [106]. The hetero­
structures, which had large surface areas and abundant oxygen va­
cancies (OVs), were synthesized by the post-oxidation of
liquid-phase-exfoliated (LPE) SnS nanosheets in air at different oxida­
tion levels, as explained henceforth.
SnS nanosheets were obtained by liquid-phase exfoliation in an
ethanol solution containing SnS powder [107] (Fig. 11). The SnS
nanosheets were dip-coated on a sensor substrate with 10-µm-wide gold
interdigitated electrodes with a gap of 5 µm. The specimens were heated
at 350–450 ◦ C to fabricate the SnOx/SnS-based gas sensor. XRD analysis
indicated that all heated samples contained SnO, SnO2, Sn2O3, Sn3O4,
and SnS, but at different amounts. The gas sensing response (S) was
defined as follows: (Rgas − Rair)/Rair × 100%. The SnOx/SnS hetero­
structures oxidized at 350 ◦ C for 1 h exhibited remarkable responses of
171% and 2735% at 1 ppb and 1 ppm NO2, respectively, which were
considerably lower than the ambient air quality guidelines established
by the WHO (20 ppb). The theoretical LOD was estimated to be 5 ppt,
according to the IUPAC definition [108,109]. This value is lower than
those of carbon-nanotube-based, metal-oxide-based, and
metal-sulfide-based sensors fabricated using materials such as WO3
[110], HOF [111], CNT [112], SnO2 [113], SnO2–SnO [114], SnO2–ZnO
[115], SnO2/graphene [116], MoS2/SnO2 [117], SnS2/SnO2 [118], SnS2
[119], SnS [120], and SnS2/SnS [121] (Table 4). The sensor responses to
500 ppm NO, CO, NH3, and H2 were 377%, 181%, − 63%, and − 55%,
respectively; moreover, the sensor showed a response of 47% to 1 ppm
SO2. Additionally, the sensor exhibited a response of − 700% at 11% RH
and a remarkable response of − 10870% at 75% RH. The SnOx/SnS gas
sensor exhibited high selectivity in low-RH environments. XRD, XPS,
SEM, TEM, electron paramagnetic resonance (EPR), and first-principles

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Table 3 the crystal growth of the SnO2-nanosheet-assembled film was based on

Previously reported responses of sensing materials to chlorine gas [84], dendritic growth. The branch angles of the nanosheets were determined
[92–104]. Reprinted with permission from ref. [84] Copyright 2021 American based on the crystal structure and growth direction. The nanosheets had
Chemical Society. two types of connections with branch angles of 90◦ (type I) and 46.48◦
Sensing materials Smax (Rgas/ Cl2 T Reference (type II) (Fig. 12d− e). The nanosheets with large (101) and (− 10 − 1)
Rair) (ppm) (℃) facets were modeled using the VESTA program [125] and the crystal
Pd-doped NiFe2O4 nanocrystals 3.33 1000 250 [92] structure data of SnO2 (COD ID:1000062) [126] (Fig. 12f). These two
Sb-doped SnO2 nanoparticles ~750.00 5 RT [93] facets, which were parallel and equivalent, contained surface-bridging
In2O3 thin film 79.30 5 250 [94] oxygen ions. The image shows four facets on the sides of the nano­
CuO- modified ZnO thick film ~194.00 300 RT [95]
MgO–In2O3 thin film ~3.20 7 275 [96]
sheet, which are the equivalent, most stable facets of (110), (− 110), (−
mesoporous SnO2 26.80 5 260 [97] 1 − 10), and (1 − 10). Molecular sensors for environmental hormones in
Te nanotubes 4.00 8 RT [98] solution and hepatocellular carcinoma have been developed using the
sulfonated copper 7.25 2 RT [99] dendritic-structured SnO2 nanosheet film [127].
phthalocyanine films
The coating of a low-heat-resistant polymer film with a metal oxide is
zinc phthalocyanine nanobelts 7.55 1.5 RT [100]
nanowires of copper 7.70 1.5 RT [101] challenging because a metal oxide, such as SnO2, requires a high tem­
phthalocyanine perature of several hundred degrees Celsius for crystallization. Howev­
CdIn2O4 powder 53,000.00 10 255 [102] er, this can be realized by crystallization in an aqueous solution. For
CdSnO3 (hydrothermal 1339.00 5 25 [103] instance, high-temperature annealing is considered indispensable in the
method)
field of ceramics. Cold crystallization, which has been a long-standing
CdSnO3 thick film 8.00 0.1 250 [104]
ZnO nanowires 3.13 5 400 [84] issue, has been realized using the aqueous solution process.
WO3 nanowires 2.90 5 250 [84]
SnO2 nanowires 1785.00 5 50 [84] 3.2. Theoretical calculations of the {110} or {101} facet of SnO2 for gas
sensing
analyses (DFT simulations) indicated that the remarkable response of
the OV-containing heterostructures to the gas molecules was possibly Theoretical calculations of the (110) or (101) facet revealed the ef­
due to the Schottky nature of the metal–SnOx/SnS system, abundant fects of different surfaces on the sensor properties. Zakaryan et al.
adsorption sites, bandgap modulation, and active electron transfer in the studied the adsorption of CO on the (110), (100), (101), and (001)
sensing interface layer. surfaces of SnO2 using DFT calculations [128] (Fig. 13). The electronic
The EPR results revealed that the intensities of the signals in the density of states combined with Bader charge analysis showed that the
samples at 325 ◦ C and 350 ◦ C were considerably higher than those (101) and (001) surface orientations gathered more electrons than the
observed at 400 ◦ C and 450 ◦ C, indicating higher OV contents at 325 ◦ C other orientations, such as (110). Moreover, the (101) or (001) surface
and 350 ◦ C. Therefore, the samples at 325 and 350 ◦ C exhibited stronger of SnO2 was determined to be a superior platform for CO gas sensing.
gas sensing responses. However, NO2 was chemisorbed on the surface of Jiang et al. conducted theoretical calculations of the (110), (101), and
the OV-containing SnOx/SnS heterostructures; the gas molecule (221) facets of SnO2 for NO and NO2 gas sensing [129]. Optimized
desorption increased in difficulty with an increase in the amount of OVs structures of the NO molecules adsorbed on the (110), (101), and (211)
on the sample surfaces. Thus, the gas response of the 325 ◦ C samples facets were obtained. The total energy was calculated using DFT to
could not be easily recovered to their initial state. Moreover, UV illu­ investigate the adsorption of NO molecules. The exchange and correla­
mination was employed to accelerate recovery. tion energies were calculated using the Perdew–Wang (PW) functional
with the generalized gradient approximation (GGA) and a double nu­
merical plus polarization (DNP) basis set. The configuration of the
3. Development of SnO2 nanosheets with cold crystallization
adsorbed NO molecule was more stable in the nitrogen orientation than
in the oxygen orientation on the (101) crystal surface. The adsorption
Morphological control of metal oxides has been actively studied
energy (binding energy) of NO on the (110) facet was the lowest,
[122]. Recently, the cold crystallization of metal oxides has been suc­
whereas that on the (211) facet was the highest. Moreover, the (101)
cessfully realized in aqueous solutions. Achieving control of aspects such
facet was found to be the most beneficial among the three crystal sur­
as crystal structure, morphology, crystal facets, crystallinity, chemical
faces for both NO and NO2 gas detection based on the determined
composition, and defects can offer scientific and industrial benefits.
adsorption energies and electron transfer. Abokifa et al. investigated
SnO2 nanosheets and dendritic-structured SnO2 nanosheet films are
the sensing mechanism of SnO2 for detecting ethanol and acetone at
discussed in this section.
room temperature using first-principles DFT calculations and ab initio
molecular dynamics (AIMD) simulations [130]. Both the ethanol and
3.1. Dendritic-structured SnO2 nanosheet film acetone molecules had stronger interactions with the pre-adsorbed O−2
species on the reduced (101) surface than on the reduced (110) surface
Cold crystallization of SnO2 was first realized in 2009 [123,124]. at room temperature. The most cited sensing mechanism involves in­
SnO2 is typically synthesized by the reaction of SnF2 and H2O in an teractions with the ionosorbed O− species that exhibit high activity for
aqueous solution. In addition, crystallization of SnO2, which typically oxidizing the target gas molecules. However, the less active superoxide
requires a high temperature of several hundred degrees Celsius, has been molecule (O−2 ) constituted the majority of the pre-adsorbed oxygen
realized at lower temperatures. Because the most stable crystal facet of species on the SnO2 surface at room temperature. Neither the ethanol
SnO2 is {110}, particles surrounded by {110} crystal facets are typically nor acetone molecules could exothermically bind to the pre-occupied
produced. However, SnO2 nanosheets with {101} crystal facets, which vacancies and showed no interactions with the pre-adsorbed O−2 spe­
are metastable crystal facets, can be synthesized by the facet-controlled cies on the reduced (110) surface. In contrast, the OV sites simulta­
growth method. Furthermore, a dendritic-structured SnO2 nanosheet neously accommodated the O−2 species and the ethanol or acetone
film has been prepared by controlling the nucleation and crystal growth molecules on the reduced (101) surface, forcing the pre-adsorbed O−2
in the solution; details of the dendritic crystal growth were clarified by species to release the minor charge back to the surface. AIMD simula­
FE-SEM (Fig. 12a− b), high-resolution TEM (Fig. 12c), and crystal tions demonstrated that both molecules preferentially bonded to the
structure models [17]. The models that were analyzed using fast Fourier unoccupied OV sites (that is, at the undercoordinated Sn4c). Once all the
transform (FFT) images and the calculated SAED pattern indicated that OV sites were filled with the pre-adsorbed oxygen from the ambient

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 11. (a) Illustration of the fabrication of the SnOx/SnS-hetero­

structure-based gas sensor. (b) XRD patterns of the as-synthesized sam­
ples. (c) SEM, (d) TEM, and (e) high-resolution TEM (HRTEM) images of
the SnOx/SnS heterostructures; the inset image in (e) shows selected area
electron diffraction (SAED) rings. Band structures of (f) SnS and (g) SnOx
determined using first-principles calculations. (h) Calculated band
alignment between SnS and SnOx, and the position of the work function
of Au. The black dashed lines represent the Fermi level, which is a
Schottky contact. Energy band structures of the SnOx/SnS heterojunction
contact with Au in (i) air and (j) a NO2 atmosphere. (k) Formation of OV-
rich SnOx/SnS heterostructure. (l) Charge density difference (CDD) plot
showing NO2 on the SnOx/SnS heterostructure. The blue and yellow re­
gions indicate charge accumulation and depletion, respectively. (m)
Electron localization function (ELF) plot of NO2 on the SnOx/SnS heter­
ostructure; an isosurface value of 0.015 e Å− 3 was used [106].
Reprinted with permission from ref [106] Copyright 2021 IOP
Publishing.

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Table 4
Comparison of various gas sensors with respect to the range of detected NO2, operating temperature, response and recovery times, and response [106], [110–121].
Reprinted with permission from ref [106]. Copyright 2021 IOP Publishing.
Sensing NO2 conc. LOD Temperature Response Recovery Response Reference
materials (ppb) (ppb) (℃) time (s) time (s) (%)

WO3 500 10 200 ~3600 ~1800 150 [110]

HOF 100 40 25 17.6 19.1 ~6.9 [111]
CNT 1 0.1 25 120 — ~25 [112]
SnO2 1 0.2 25 ~1800 ~900 ~90 [113]
SnO2–SnO 100 100 50 ~150 ~400 26 ppm− 1 [114]
SnO2–ZnO 400 — 200 ~300 ~300 600 [115]
SnO2/graphene 10 0.024 150 43 408 200–300 [116]
MoS2/SnO2 500 — 25 408 162 0.6 [117]
SnS2/SnO2 125 — 100 299 143 ~90 [118]
SnS2 10,000 — 120 ~170 ~140 ~3600 [119]
SnS 1000 — 25 ~25 ~25 60 [120]
SnS2/SnS 400 75 25 365 1216 660 [121]
SnOx/SnS 1 0.005 25 1800 36 (UV) 171 [106]
SnOx/SnS 1000 0.005 25 1800 36 (UV) 2735 [106]

CNT: carbon nanotube, HOF: hydrogen-bonded organic framework material.

atmosphere, the target molecule tended to momentarily share the pre­
occupied vacancies with the pre-adsorbed oxygen molecules prior to its
eventual binding to the surface Sn5c sites. Therefore, the adsorption
configuration resembled that of stoichiometric surfaces. Additionally,
the authors reported that adsorption was generally stronger for ethanol
than for acetone because of the bipolar nature of the hydroxyl group (in
ethanol) that interacted with the surface via two distinct charge-transfer
modes. These results suggest that the sensing mechanism of SnO2 for
polar VOCs at room temperature can be explained by their direct
adsorption on the surface rather than through oxidation by the ion­
osorbed oxygen species. Feng et al. investigated the relationship be­
tween the morphology and humidity sensing properties of SnO2 using
DFT calculations [131]. The calculations indicated that the {101} facet
adsorbed more water molecules than the {110} facet. This result was
consistent with the experimental data obtained using a nanosensor
based on three-dimensional (3D) hierarchical SnO2 dodecahedral
nanocrystals (DNCs), which exhibited superior humidity-sensing per­
formance, including fast response and recovery times, narrow hysteresis
loop, high sensitivity, excellent linearity response, and decent stability,
compared with those of 3D hierarchical SnO2 nanorods (NRs) and SnO2
nanoparticles (NPs). The authors attributed the enhanced sensing
properties of the DNCs to the peculiar 3D open nanostructures and high
chemical activity of the exposed {101} facet. In summary, 3D open
nanostructures can promote the penetration and diffusion of water
molecules, and the exposed {101} facet can facilitate their adsorption.
3.3. SnO2 nanosheet/SnO2 nanoparticle film with Pt, Au, and Pd for 1-
nonanal/lung cancer detection
Several types of gas sensors and odor sensors have been developed
using dendritic-structured SnO2 nanosheet films, as discussed below.
These dendritic-structured films were was shown to exhibit excellent
performance as a gas sensor and as a molecular sensor in a solution.
The exhaled breath of lung cancer patients is known to contain a
higher concentration of nonanal molecules than that of healthy in­
dividuals. Therefore, the use of gas sensors to screen for lung cancer can
offer tremendous benefits. A representative nonanal-detecting gas
sensor was fabricated by first preparing a SnO2-nanoparticle film con­
taining nanoparticles of Pt, Au, and Pd as a catalyst on the sensor sub­
strate as the first layer [132] (Fig. 14a). The substrate was immersed in a
SnF2 aqueous solution to grow SnO2 nanosheets on the surface of the
SnO2-nanoparticle film. The gas sensor showed an increased response
with increasing concentration of nonanal. In particular, the SnO2
nanosheet showed an improved rate of increase in the response to an
increase in the nonanal concentration from 1 to 10 ppm (Fig. 14b).
3.4. SnO2-nanosheet-based MEMS
[lung cancer detection].
An MEMS-type gas sensor was subsequently developed using SnO2
nanosheets [133], which were crystallized on a Si3N4 (SIN) substrate on
which a Pt electrode and a Pt heater were formed. The MEMS sensor was
evaluated at 250 ◦ C (Fig. 15). The SnO2-nanosheet-type sensors
exhibited superior response (Ra/Rg) to nonanal (C9H18O), a lung cancer
marker, compared to that of CO, nitrogen dioxide (NO2), acetone
(CH3COCH3), hydrogen (H2), ethanol (C2H6O), ammonia (NH3),
hydrogen sulfide (H2S), formaldehyde (HCHO), acetaldehyde
(CH3CHO), and butyraldehyde (C4H8O). In addition, the responses to
various aldehydes were evaluated. The results showed that the response
increased with increasing molecular weight in the order of formalde­
hyde (HCHO), acetaldehyde (CH3CHO), butyraldehyde (C4H8O,
C3H7CHO), and nonanal (C9H18O, C8H17CHO). The response to nonanal
increased from 1.383 for 100 ppb to 2.00 for 300 ppb, showing a strong
concentration dependence. The high sensitivity and molecular recog­
nition characteristics of the SnO2 nanosheets to nonanal molecules
enable the early detection of lung cancer.
3.5. H2/CH4 sensing properties of the dendritic-structured SnO2
nanosheet film
The most thermodynamically stable crystal facet of tin oxide is
{110}. However, the large surface of the SnO2 nanosheets has a meta­
stable {101} facet, which is a characteristic feature of these nanosheets.
Choi et al. studied the anisotropic growth of SnO2 nanosheets and the
effects of crystal facets on gas sensing properties [134] (Fig. 16).
Time-varying XRD analysis of the crystallite size revealed that the ver­
tical growth of the {101} facet of the SnO2 nanosheets was suppressed
and that the growth proceeded in the in-plane direction. In addition, XPS
analysis revealed that the SnO2 nanosheets contained Sn2+ in addition to
Sn4+. Moreover, the presence of several OVs in the SnO2 nanosheets was
confirmed. These features assisted in enabling the excellent sensor
response. Furthermore, the H2 and CH4 gas sensing characteristics were
evaluated using rectangular SnO2 particles with the {110} facet and
SnO2 nanosheets. The response to CH4 was 1.5 for the SnO2 particles
with the {110} facet, whereas that of the SnO2 nanosheets was slightly
lower at 1.3. However, the response of the SnO2 particles to H2 was 3.0,
whereas that of the SnO2 nanosheets was 7.5, which was more than
double the former. Moreover, the 90% response time (T90 response) and
90% recovery time (T90 recovery) to reach 90% of the saturation
resistance in the gas and air were evaluated. The SnO2 particles showed
T90 responses of 24 s and 18 s for H2 or CH4, respectively, whereas the
SnO2 nanosheets showed fast response times of 18 s and 6 s,

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Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 12. Surface (a) and cross-sectional (b) SEM images of the SnO2
(101)-nanosheet-assembled film. (c) Cross-sectional TEM image of the
SnO2 (101)-nanosheet-assembled film. (d) Cross-sectional TEM image of
the gradient structure of the SnO2 (101)-nanosheet-assembled film on an
FTO substrate with branch angles of 90◦ (type I; red circle) and 46.48◦
(type II; blue circle) between the SnO2 nanosheets. (e) Crystal growth
models of the SnO2 nanosheets that were connected at branch angles of
90◦ (right, red circle) and 46.48◦ (left, blue circle), respectively. The
models were observed from the direction of B = <1 − 1 − 1 > of SnO2.
(f) Model of the SnO2 nanosheet with large (101) and (− 10 − 1) facets
[17]. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
Reprinted with permission from ref [17] Copyright 2021 Springer
Nature.

17
Y. Masuda
Fig. 13. Different surfaces of SnO2 featuring possible adsorption sites: (a) -
(110), (b) - (100), (c) - (101), and (d) - (001) [128].
Reprinted with permission from ref [128] Copyright 2021 International Fre­
quency Sensor Association (IFSA) Publishing.
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Sensors and Actuators: B. Chemical 364 (2022) 131876
respectively. The SnO2 particles showed T90 recoveries of 36 s and 44 s
for H2 and CH4, respectively, whereas the SnO2 nanosheets showed fast
recovery times of 28 s and 12 s, respectively. Further clarification of the
characteristics of the SnO2 nanosheets can facilitate the development of
highly sensitive gas sensors and odor sensors.
3.6. The dendritic-structured SnO2 nanosheet film
[200-ppb-acetone sensing].
Detection of low-concentration acetone in gases that are exhaled and
released via skin can enable early detection of diabetes. In addition,
acetone detection is crucial for monitoring odors in rooms. Kim et al.
developed a low-concentration acetone gas sensor using a dendritic-
structured SnO2 nanosheet film [135] (Fig. 17a). The size and aspect
ratio of the SnO2 nanosheets were controlled by varying the duration of
synthesis. The effects of the synthesis period on sensor characteristics
were evaluated. The dendritic-structured SnO2 nanosheet film synthe­
sized by crystal growth over 6 h exhibited a superior response than those
of films synthesized for 2 h or 24 h. The operating temperature of the
sensor was investigated in the range of 200–300 ◦ C, with an excellent
response being obtained at 280 ◦ C. Detection of low-concentration
acetone gas was realized using the dendritic-structured SnO2 nano­
sheet film synthesized for 6 h (Fig. 17b− d). A response value of
approximately 3 was achieved for 200 ppb acetone (Fig. 17e− f). Addi­
tionally, the response to 1 ppm acetone reached 10.2, which is higher
than the acetone response values of the other SnO2 sensors, such as
porous flower-like SnO2 [136], hierarchical SnO2 hollow microspheres
[137], SnO2 microspheres with Au and NiO [138], co-catalyzed SnO2
nanospheres [139], nanotubular SnO2 [140], and mesoporous SnO2
[141] (Table 5). In addition, the gas selectivity was analyzed. The
response to 1 ppm acetone (10.2) was higher than those for 1 ppm
acetaldehyde, isoprene, xylene, cyclohexane, toluene, or ammonia (1–3;
Fig. 17g− h). As mentioned earlier, the dendritic-structured SnO2
nanosheet film was confirmed to exhibit a high sensitivity for detecting
low-concentration acetone (200 ppb) and a high gas selectivity in terms
of selectively detecting acetone from a plurality of gases. The
dendritic-structured SnO2 nanosheet film can be effectively employed to
detect diabetes and for indoor air management.
3.7. Bridge-type dendritic-structured SnO2 nanosheet film
3.7.1. [lung cancer detection]
Choi et al. developed a bridge-type dendritic-structured SnO2
nanosheet film [142], which was separated from the substrate by
approximately 100 nm (Fig. 18a). A SiO2 substrate with comb-shaped Pt
electrodes was used for sensing. The space was formed between the
bridge-type dendritic-structured SnO2 nanosheet film and the SiO2
substrate owing to the etching effect of SiO2 in the aqueous SnF2 solu­
tion. For comparison, a SnO2 dendritic-structured nanosheet film was
also formed on an alumina substrate with a comb-shaped Pt electrode
(Fig. 18b). Approximately 150-nm-thick dendritic-structured SnO2
nanosheet films were synthesized in both scenarios by immersion in an
aqueous SnF2 solution (28 mM, 90 ◦ C) for 6 h. The effects of the bridge
structure were examined by comparing the two SnO2 nanosheet films
(Fig. 18c). The bridged version exhibited superior responses to hydrogen
(500 ppm), methane (500 ppm), and nonanal (0.85 ppm) than those of
the SnO2-based film on the alumina substrate. Both sides of the bridge
structure membrane were presumed to participate in the reaction with
the gas. In addition, the space under the bridge structure was considered
to function as a reaction field for additional oxidation of partially
oxidized molecules. The bridge-type dendritic-structured SnO2 nano­
sheet film showed a stronger response to hydrogen than to methane. In
addition, considering the employed gas concentration, the response to
nonanal was considerably superior to those of hydrogen and methane.
The bridge-type dendritic-structured SnO2 nanosheet film had a unique
structure, and both sides of the film were in contact with the gas, which
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 14. (a) Schematic view of the reaction of a 1-nonanal molecule on a sensor consisting of SnO2 nanosheets, SnO2 nanoparticles, and noble metal catalysts. (b)
Changes in sensitivity with 1-nonanal gas concentration for NS(6 h)/PF (solid circles and lines) and PF (open circles and dotted lines) at 250 ◦ C and 300 ◦ C (blue and
red profiles, respectively; NS: SnO2 nanosheet, PF: SnO2 particulate film). (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
[132] Reprinted with permission from ref [132] Copyright 2021 Springer Nature.

Fig. 15. (a) Photograph of a sensor containing

three micro sensor tips. (b) Photograph of
sensor tip array, with the inset showing a
magnified photograph of the sensor tip. (c) SEM
micrograph of the sensor tip. Magnified SEM
micrograph of the sensor tip showing the SiN
(d) and Pt areas (e). B, Magnified SEM micro­
graph of SnO2 nanosheets in the SiN area. (f)
Sensor sensitivities to carbon monoxide, nitro­
gen dioxide, acetone, hydrogen, ethanol,
ammonia, hydrogen sulfide, formaldehyde,
acetaldehyde, and nonanal; a nonanal concen­
tration of 0.1 ppm at 250 ◦ C was used. (g)
Change in sensitivity with aldehyde carbon
number in a series featuring formaldehyde,
acetaldehyde, butanal, and nonanal; a nonanal
concentration of 0.3 ppm at 250 ◦ C was used
[133].
Reprinted with permission from ref. [133]
Copyright 2021 John Wiley and Sons.

facilitated the reaction with the target molecules. In addition, the film
had a space between the substrate for gas trapping. These characteristics
are effective for sensing molecules that have a large molecular weight
and cannot readily undergo complete oxidation, such as nonanal.
3.8. Surface molecular separator for selective gas sensing
Choi et al. introduced a metal–organic framework (MOF) layer of
zeolitic imidazolate framework-8 (ZIF-8) on the surface of a SnO2
nanosheet sensor [143]. The MOF layer functioned as a surface

19
Y. Masuda
Fig. 16. (a) Variation in crystallite size perpendicular to the (110), (101), and (211) planes of a SnO2 nanosheet as a function of growth period. (b) Primary growth
direction of a SnO2 nanosheet. XPS profiles of the SnO2 nanosheet and the SnO2 nanoparticle gas sensors: O-1 s data of the (c) nanosheets and (d) nanoparticles.
Cross-sections of crystal structure models of the (e) (110) surface of the SnO2 nanoparticles and the (f) (101) surface of the SnO2 nanosheets [134].
Reprinted with permission from ref [134] Copyright 2021 Elsevier.
molecular separator for selective gas sensing, and the gas selectivity of
the sensor was analyzed, as described below.
The bridge-type SnO2 nanosheet sensors were dipped into a 0.1 M
aqueous zinc nitrate solution and heated at 200 ◦ C for 6 h to form a ZnO
seed layer. The resulting product was immersed in an aqueous solution
containing zinc nitrate hexahydrate and 2-methylimidazole at 50 ◦ C for
4 h to grow a ZIF-8 layer (Fig. 19). ZIF-8 operates as a molecular sieve
for approximately 4.0–4.2-Å-sized particles. Compared to the SnO2-
nanosheet-based gas sensor, the ZIF-8/SnO2-nanosheet equivalent
exhibited a decreased signal response for large molecules, for example,
C3H6 (4.120 Å), 1-C4H8 (5.430 Å), and C9H18O (12.011 Å) (Fig. 19g− i).
However, the response of the ZIF-8/SnO2-nanosheet-based sensor to
smaller gas molecules, such as C2H4 (3.058 Å), slightly increased owing
to electron transfer at the ZIF-8–SnO2 interface. The control of gas
selectivity based on molecular size was realized by introducing ZIF-8 as
a surface molecular separator.
Gas selectivity achieved via introduction of ZIF-8 can be classified
into two categories (Table 6); one involves an increase in the sensor
signal response to target gases, and the other involves a decrease in the
signal response to nontarget gases. In the former case, ZIF-8 contributes
to an enhancement of the gas selectivity to relatively small gas mole­
cules, such as H2 and NO2. This enhancement effect can be monitored
using the response ratio (SM/SM+ZIF-8), which is calculated using the
sensor signal responses before (SM) and after (SM/SM+ZIF-8) the
introduction of ZIF-8. The response ratios of ZnO@ZIF-8 for 5, 10, 50,
100, 200, and 500 ppm CH3CH2OH were reported to be 0.92, 0.62, 0.40,
0.41, 0.43, and 0.41, respectively [144], whereas those of pristine ZnO
were approximately 3.39, 4.80, 11.27, 14.54, 19.98, and 32.0, respec­
tively. In contrast, responses of approximately 3.68, 7.70, 28.13, 35.90,
46.65, and 78.0 were observed at the aforementioned ethanol concen­
trations for the ZnO@ZIF-8 core–shell material. Moreover, the response
ratio of ZnO@ZIF-8 nanorods to 50 ppm H2 was 0.67 [145]. The
ZnO@ZIF-8 nanorods exhibited a higher H2 sensitivity than that of the
pristine ZnO nanorods at 250 ◦ C (Ra/Rg = 2.15 and 3.28, respectively, at
50 ppm). The response ratio of ZIF-8-coated In2O3 composite fibers
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Sensors and Actuators: B. Chemical 364 (2022) 131876
(In2O3:ZIF-8 = 4:1) for 1 ppm NO2 was 0.3 [146]. The
operating-temperature-dependent results for 1 ppm NO2 showed that
the optimal testing temperature for In2O3/ZIF-8 was 140 ◦ C, which was
slightly lower than that for pristine In2O3 nanofibers (160 ◦ C). The
In2O3/ZIF-8 (4:1)-based sensor exhibited the highest NO2 response,
followed by In2O3/ZIF-8 (2:1), In2O3/ZIF-8 (8:1), and pristine In2O3 NFs
at 140 ◦ C (Rg/Ra = 16.4, 10.7, 10.4, and 4.9, respectively). Moreover,
the response ratio of the ZIF-8/SnO2 nanosheets to 50 ppm C2H4
reached 0.85. The sensor signal response to C2H4, a small gas molecule,
increased after the introduction of ZIF-8, similar to trends described in
previous reports [145–147]. This enhancement was presumably caused
by the improvement of the activity, which was attributed to the changes
in electrons at the interface between the sensor material and ZIF-8.
In addition, the separation effect has been reported in previous
studies. The responses of pristine ZnO nanowires to 10, 30, and
50 ppm H2were 2.34, 2.47, and 2.62, respectively, [148] which
decreased to 1.17, 1.34, and 1.44, respectively, for the ZnO@ZIF-8
nanowires. The response ratios (SM/SM+ZIF-8) for 10, 30, and
50 ppm H2 were 2, 1.84, and 1.82, respectively. The pristine ZnO
nanowires responded to C6H6 and C7H8; however, the responses of the
ZnO@ZIF-8 nanowires to C6H6 and C7H8 almost vanished and
approached 1.0. The response ratios (SM/SM+ZIF-8) for 10, 30, and
50 ppm C6H6 and 10, 30, and 50 ppm C7H8 were calculated to be 1.33,
1.43, 1.58, and 1.24, 1.29, and 1.40, respectively. The response ratios of
the ZnO@ZIF-8 nanorod arrays for 50 ppm H2, NH3, CH3CH2OH,
CH3COCH3, and C6H6 were 1.12, 1.25, 5.5, 7, and 7, respectively, [149].
ZIF-8-coated Pd/ZnO nanowires were reported to have response ratios
of 1.28, 2.75, 4.70, 3.50, and 3.30 for 50 ppm H2, CH3CH2OH,
CH3COCH3, C6H6, and C7H8, respectively; [150] those of the ZIF-8/SnO2
nanosheets (SM/SM+ZIF-8) for 50 ppm C3H6, C4H8, and C9H18O were
1.18, 1.67, and 2.15, respectively. In the case of a decreasing signal
response, ZIF-8 enabled the separation by operating as a molecular
sieve. Although decreases were observed in the sensor signal responses
to both large and small gas molecules, the sensor signal response to large
gas molecules decreased considerably. In addition, no sensor signal
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 17. (a) Schematic of SnO2 nano­

sheet. (b) Cross-sectional TEM image of
the dendritic-structured SnO2 nanosheet
film, (c) HR-TEM image of a single
nanosheet, and (d) atomic arrangements
in a single nanosheet. (e) Dynamic
response curve of NS-6 from 200 to 1000
ppb, (f) responses of NS-6 from 200 to
1000 ppb, (g) responses of NS-
6–1000 ppb acetone, acetaldehyde,
isoprene, xylene, toluene, and ammonia,
and (h) appearance energies of acetone,
acetaldehyde, isoprene, xylene, and
toluene (excluding cyclohexane and
ammonia) for the dissociation of a
methyl cation [135].
Reprinted with permission from ref.
[135] Copyright 2021 American Chemi­
cal Society.

21
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Table 5
Various types of SnO2-based acetone gas sensors and their responses to specific
concentrations [135], [136–141]. Reprinted with permission from ref [135].
Copyright 2021 American Chemical Society.
Sensing material Acetone conc. Response Refecence
(ppm)

porous flower-like SnO2 20 30 [136]

hierarchical SnO2 hollow microspheres 20 2.4 [137]
SnO2 microsphere with Au and NiO 1 5 [138]
Co-catalyzed SnO2 nanosphere 1 1.8 [139]
nanotubular SnO2 1 1.6 [140]
mesoporous SnO2 1 1.5 [141]
SnO2 nanosheet 1 10.2 [135]

responses were recorded for certain large gas molecules after ZIF-8
introduction under several conditions [148,150]. In these studies, the
sensor signal response to large gas molecules, such as C3H6, C4H8, and
C9H18O, decreased after ZIF-8 introduction, which was mainly attrib­
uted to the molecular sieving effect of ZIF-8. The dominant effect of the
enhancement or separation of ZIF-8 on gas sensing is possibly influenced
by various factors such as thickness and operating temperature. By
controlling these factors, an effective improvement in gas selectivity can
be realized via the introduction of a molecular separation layer, such as
ZIF-8. This variation in selectivity with the molecular size of the gas can
facilitate the identification of gas species by data processing. In partic­
ular, the ZIF-8/SnO2 nanosheet thin film can be applied in the medical
field to improve the reliability of selective detection of biomarkers, such
as the C9H18O lung cancer biomarker.

4. Conclusion

Various SnO2 nanomaterials have been developed to improve the

sensitivity, response speed, selectivity, and durability of sensors. Low-
concentration gas sensing is crucial for the detection of biological
gases and spatial odor, which require further improvements in sensi­
tivity. Control of nanostructures, crystal planes, and defects is pro­
gressing, and the acquired information can be leveraged for the
development of materials other than SnO2. This review is anticipated to
facilitate the development of advanced high-sensitivity gas sensors and
odor sensors for solving problems related to healthcare, indoor air
control, food transportation and storage, and plant safety and
construction.
Recent advances in SnO2 nanostructure based gas sensors suggest
valuable guidelines for development of SnO2 nanostrures. It is revealed
that dimension and morphology affect the sensing performance with
reported studies. The following are important guidelines. Crystallite
sizes of oxide semiconductors should be as small as possible. Sensitizers
should be dispersed as finely as possible. Sensing layer thickness and
porosity should also be optimized to improve selectivity and durability.
Furthermore, state-of-the-art liquid phase crystal growth control
technology has made it possible to control the SnO2 nanostructure. This
has made it possible to realize the following design guidelines for the
development of SnO2 nanomaterials. SnO2 nanomaterials having nano-
meter size which is similar to size of a depletion layer, and controlled
microstructure such as a nanosheet structure shows high sensing per­
formance. The dendritic structure in which 2D nanosheets are connected
by crystal growth points the direction for future sensor development.
Furthermore, the high gas adsorption performance and reactivity of the
metastable crystal plane will be a guide for future sensor development.
Metal oxide semiconductor-type gas sensors have advantages for
detecting low concentration gases. However, gas selectivity of them is
not enough high. Control of surface crystal facet, crystal defects,
Fig. 18. Schematic illustrations of sensing reaction for a (a) SnO2 nanosheet
thin film with a bridge-type structure (BS) and a (b) typical SnO2 nanosheet thin
film on a Pt interdigitated-electrodes-printed Al2O3 substrate (NS). (c) Sensor
response ratios of BS to NS for 500 ppm H2, 500 ppm CH4, and
0.85 ppm C9H18O gases [142].
Reprinted with permission from ref. [142] Copyright 2021 Elsevier.
nanostructures, etc. can be applied to improve the selectivity. Surface
modification with nanomaterials including metal oxides, polymers, self-
assembled monolayers, carbon materials, etc. can be also utilized. MOF
surface molecular separator, p-n hybrid structures, temperature control
of the sensor, excitation light will be helpful. Additionally, one of the
resolutions for the issue is sensor array which includes various type of
metal oxide semiconductor-type gas sensors with/without different type
sensors. Sensing signals, which are obtained from the sensors, can be
analyzed to recognize gas or odor automatically with AI or machine
learning techniques. Furthermore, MEMS type sensors have advantages
in low power consumption, miniaturization, and weight reduction. The
heating elements are connected by narrow bridges to float in some
MEMS devices. Therefore, the MEMS devices have the advantage that

22
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Fig. 19. (a) Schematic diagram of the interactions between ZIF-8 and SnO2 nanosheets. (b) Surface FE-SEM image and (c) a cross-section TEM image of the ZIF-8/
SnO2 nanosheet thin film. (d) HAADF-STEM image and STEM-EDS mappings of the ZIF-8/SnO2 nanosheet thin film: Sn (e) and Zn (f). Variations in the (g) electrical
resistance, (h) sensor signal response, and (i) response ratio of the SnO2 nanosheet thin-film and ZIF-8/SnO2 nanosheet thin-film gas sensors for 50 ppm C2H4, C3H6,
and C4H8, and 0.85 ppm C9H18O. (j) Crystal structure of ZIF-8 and molecular structures of (k) C2H4, (l) C3H6, (m) C4H8, and (n) C9H18O [143].
Reprinted with permission from ref [143] Copyright 2021 American Chemical Society.

23
Y. Masuda Sensors and Actuators: B. Chemical 364 (2022) 131876

Table 6
Comparison of previously reported ZIF-8-incorporated metal oxide gas sensors [143], [144–146,148–150]. Reprinted with permission from ref [143]. Copyright 2021
American Chemical Society.
Sensing materials Temp. Target gas Conc. Response ratioa Ref.
(℃) (ppm) (SM/SM+ZIF-8),
Response of SM,
Response of SM+ZIF-8

enhancement ZnO@ZIF-8 160 CH3CH2OH 5 0.92 (3.39/3.68) [144]

10 0.62 (4.80/7.70)
50 0.40 (11.27/28.13)
100 0.41 (14.54/35.90)
200 0.43 (19.98/46.65)
500 0.41 (32.0/78.0)
ZnO@ZIF-8 nanorods 250 H2 50 0.66 (2.15/3.28) [145]
ZIF-8-coated In2O3 composite fibers 140 NO2 [146]
(In2O3:ZIF-8 =4:1) 1 0.30 (4.9/16.4)
(In2O3:ZIF-8 =2:1) 1 0.46 (4.9/10.7)
(In2O3:ZIF-8 =8:1) 1 0.47 (4.9/10.4)
ZIF-8/SnO2 nanosheets 100 C2H4 50 0.85 [143]
separation ZnO@ZIF-8 nanowires 300 H2 10 2 (2.34/1.17) [148]
30 1.84 (2.47/1.34)
50 1.82 (2.62/1.44)
C6H6 10 1.33b (1.33/1)
30 1.43b (1.43/1)
50 1.58b (1.58/1)
C7H8 10 1.24b (1.24/1)
30 1.29b (1.29/1)
50 1.40b (1.40/1)
ZnO@ZIF-8 nanorod arrays 250 H2 50 1.12 [149]
NH3 50 1.25
CH3CH2OH 50 5.5
CH3COCH3 50 7
C6H6 50 7
ZIF-8-coated Pd/ZnO nanowires 200 H2 50 1.28 [150]
CH3CH2OH 50 2.75b
CH3COCH3 50 4.70b
C6H6 50 3.50b
C7H8 50 3.30b
ZIF-8/SnO2 nanosheets 100 C3H6 50 1.18 [143]
C4H8 50 1.67
C9H18O 50 2.15
a
SM and SM+ZIF are the sensor signal responses before and after introduction of ZIF-8, respectively.
b
No sensor signal response after incorporation of ZIF-8.

they do not get hot and do not affect the surrounding devices. Some of
these techniques have been introduced in this review. I hope that these
technologies will help to detect low-concentration gases and odors in the
healthcare and environmental fields.
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.
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