Sensors and Actuators A 309 (2020) 112026

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Sensors and Actuators A: Physical

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

Metal oxide semiconductors with highly concentrated oxygen

vacancies for gas sensing materials: A review
Chao Zhang a,∗ , Guifang Liu a , Xin Geng b , Kaidi Wu a , Marc Debliquy c
a
College of Mechanical Engineering, Yangzhou University, Yangzhou 225127, China
b
Department of Chemistry, Wayne State University, Detroit 8202, United States
c
Service de Science des Matériaux, Faculté Polytechnique, Université de Mons, Mons 7000, Belgium

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

Article history: The introduction of oxygen vacancies into metal oxide semiconductors is an effective way to enhance
Received 29 March 2020 their gas sensing performance. In this review paper, firstly, the roles of oxygen vacancies on band struc-
Received in revised form 23 April 2020 ture, electrical conductivity, optical absorption and gas adsorption are presented. The presence of highly
Accepted 23 April 2020
concentrated oxygen vacancies narrows the bandgap width of semiconductors, thus reducing the energy
Available online 30 April 2020
required for electron transition. It also increases the active sites on the material surface and enhances the
chemisorption, thus improving the adsorption performance of the material. In addition, it also improves
Keywords:
the electrical conductivity and light absorption ability of the material. Then, this review paper briefly
Gas sensor
Metal oxide
introduced the state of the art of metal oxide semiconductors with highly concentrated oxygen vacan-
Semiconductor cies fabricated by various processes, which are mainly divided into direct and indirect methods. At last,
Oxygen vacancy the application of metal oxide semiconductors with highly concentrated oxygen vacancies in the field of
gas sensors is reviewed.
© 2020 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Roles of oxygen vacancy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Generalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Band structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.3. Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.4. Optical absorption spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.5. Adsorption and surface reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Ways to introduce oxygen vacancy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Direct introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Indirect introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Applications in gas sensing materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5. Conclusions and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Biography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

∗ Corresponding author.
E-mail address: zhangc@yzu.edu.cn (C. Zhang).

https://doi.org/10.1016/j.sna.2020.112026
0924-4247/© 2020 Elsevier B.V. All rights reserved.
2 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
1. Introduction
In the early 50s, two scientists at Bell Labs, Brattain, and Bardeen
[1] demonstrated for the first time that the conductivity of some
semiconductor materials, such as Ge, would change regularly due
to the adsorption and desorption behavior of gases at their sur-
face. The conductivity change is due to the reversible doping of
the surface by the adsorbed gas. In 1962, ZnO nanomaterials were
successfully prepared by Seiyama et al. [2], revealing that the gas
sensing device based on ZnO thin film can detect different gases at
485 ◦ C. At that time, the gas detection mainly used thermal con-
ductivity detectors, and the sensitivity of ZnO films to propane was
much higher than that of thermal conductivity detectors. It is the
beginning of the long story of the metal oxide semiconductor gas
sensors. Those sensors showed high sensitivity to a large number
of gases but unfortunately must be operated at high temperature
as the adsorption–desorption and surface reactions are generally
too slow at room temperature.
In recent years, metal oxide semiconductor materials have
attracted much attention in gas sensors. Using semiconductor
materials to fabricate gas sensors has many advantages, for exam-
ple, the small size, the low cost, and ease of maintenance [3].
However, the current semiconductor materials are mostly wide-
bandgap semiconductors, requiring energetic operating conditions.
Most of them require high temperature or ultraviolet light to excite
their valence band electrons, which make them difficult to be
applied in practical applications [4]. Researchers have been seek-
ing ways to enhance the gas-sensitive properties of metal oxide
semiconductor materials at room temperature. A large number
of studies have shown that doping [5–7], constructing a special
microstructure [8,9], compositing p-type semiconductor and n-
type semiconductor to form heterojunction [10,11] or introducing
oxygen vacancies [12] can effectively improve the performances,
and introducing oxygen vacancies does not require the addition of
other elements, the cost is low and the operation is simple. There-
fore, it is an important research direction to enable semiconductor
materials to work at room temperature or visible light through
oxygen vacancy self-doping [13,14]. Narrowing the bandgap of
wide-bandgap semiconductor materials by oxygen vacancy self-
doping is a key part of the large-scale application of semiconductor
materials. Compared with methods such as metal element doping
[15–17], second phase modification [18,19] and dye sensitization
[20–22], oxygen vacancy self-doping is the most straightforward
method to adjust the forbidden bandwidth of metal oxide semi-
conductors, and the cost is relatively low. Moreover, if the method
of multiple means can be utilized, it is possible to complement each
other and obtain a semiconductor material with excellent perfor-
mances. In this article, the focus will be put on the effect of metal
oxides with high oxygen vacancies on metal oxide semiconduc-
tors for gas detection. The ways to introduce oxygen vacancies
and the applications of metal oxide semiconductors with highly
concentrated oxygen vacancies on gas sensors are also introduced.
2. Roles of oxygen vacancy
2.1. Generalities
The oxygen vacancy generation process is usually accompanied
by a series of physical/chemical changes, for instance, changes in
the Fermi level, bond rupture and remodeling and lattice distor-
tion. The addition of oxygen vacancies could create a new energy
level and when the oxygen vacancies reach a certain concentration
(>0.1%), the energy bands can be deeply modified in comparison
with the pristine material. For transition metal oxide semiconduc-
tors (the most used in practical applications), the valence band
(VB) mainly consists of the 2p orbital of O. The conduction band
(CB) mainly comes from the d orbital of the metal. Therefore, the
introduction of donor defects such as oxygen vacancies causes the
valence band change of the semiconductor material. Changes in
the energy band results will cause changes in the material’s optical
absorption properties.
The electrical properties of metal oxides are generally associ-
ated with defects in the crystal lattice [23–25]. The introduction
of oxygen vacancies will increase the carrier concentration inside
the material, thus affecting the electrical properties. Due to the
existence of oxygen vacancies, a large number of unpaired elec-
trons appear on the surface, which increases the active site, thereby
increasing the adsorption performance of the material.
2.2. Band structure
Most of the simple metal oxides (SnO2 , ZnO, In2 O3 , WO3 , TiO2 )
have a significant gap (>2 eV) and are thus insulating in the state of
perfect crystal [26–28]. The reason for these defects is, on the one
hand, the incorporation of impurities, and on the other hand, the
non-stoichiometric relationship that can exist between the cations
and anions.
For example, the NiO is a p-type semiconductor. Indeed, some
nodes Ni2+ networks are vacant and to keep the electroneutral-
ity, an equivalent number of Ni2+ ions lose one valence electron.
Formed holes are responsible for the electrical conductivity. ZnO is
a kind of n-type semiconductor. This is due to an excess of atomic
Zn in the interstitial position. These atoms can be easily ionized,
liberating electrons favoring the current transport. SnO2 , In2 O3 ,
TiO2, WO3 are in this family. Another class of semiconductors is
that of metal oxides with the same element can have different
valences. Relevant oxides are the Fe3 O4 , Co3 O4 , Cu2 O, and so on.
At higher temperatures, gaps and the atoms in the interstitial posi-
tion can move and participate in the movement of charge carriers,
greatly complicating the conductivity phenomena. In most appli-
cations, the materials work at low temperatures (< 500 ◦ C), so the
contribution of ionic conductivity cannot be neglected.
In the classical band theory, the “defects” introduce discrete
energy levels (if the amount of defects remains low) in the band
of the material. These levels can be donor or acceptor depend-
ing on the nature of the defect. Therefore, the introduction (often
involuntary) of defects provokes the creation of charges carriers,
free electrons or holes. These introduced carriers condition most
electric and optical properties of the material.
Taking the example of the widely used n-type metal oxides, the
vacancy levels formed by oxygen vacancies work as a bridge in the
excitation transition of electrons and act as electron donor levels.
Naldoni et al. [29] noted in their article that after hydrogenation
of TiO2 , not only the broadening and upshift of the valence band
top occurred, but also a new donor vacancy level was formed in
the forbidden band. Wang et al. [30] also reduced TiO2 in a hydro-
gen atmosphere to produce arrays of high specific surface area
and donor vacancy density. The arrays exhibit good absorption of
ultraviolet light and achieve absorption of visible light, indicating
that the bandgap of TiO2 is narrowed. However, the valence band
edge energy of the three groups of hydrogenated TiO2 materials
at different temperatures is about the same as that of the pristine
TiO2 , which is about 1.2 eV. In other words, the hydrogen reduction
treatment did not widen the top edge of VB of TiO2 . According to
these results, Wang established a schematic diagram of the TiO2
energy level. As shown in Fig. 1 the oxygen vacancies obtained by
hydrogenation formed new donor levels in the forbidden band.
Li et al. [31] calculated the state density of Ti4+ -3d, Ti3+ -3d, O-2p
of TiO2 , predicted electronic structure by first-principle calcula-
tion, and studied the relationship between oxygen vacancy and
bandgap width. Li et al. proposed that the bandgap width of TiO2
 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
Fig. 1. Oxygen vacancies formed new energy levels. Reprinted with permission from
Ref. [30]. Copyright 2011, American Chemical Society.
did not change after the introduction of oxygen vacancies, and the
enhancement of the absorption of visible light is provided by the
new energy level in the forbidden band formed by oxygen vacan-
cies. The introduction of oxygen vacancies causes unpaired excess
electrons to appear inside the TiO2 crystals, and these extra elec-
trons will be trapped by Ti4+ to form Ti3+ . The empty t2g orbital of
TiO2 forms its conduction band bottom. When oxygen vacancies
are introduced, the corresponding excess unpaired electrons are
filled into the empty t2g orbital, and a new level will be formed.
Not only TiO2 , but the introduction of oxygen vacancies also has
a similar effect on the bandgap of other metal oxide semicon-
ductor materials. Wang et al. [32] used ZnO2 as a precursor and
annealed at different temperatures to obtain ZnO materials with
a set of concentration gradients of oxygen vacancies. According to
the first principle, how the concentration of oxygen vacancies influ-
ences the band structure of ZnO is calculated. The results show
that when oxygen vacancies are introduced, a new vacancy state
level is formed in the valence band (near the top edge). When the
concentration of oxygen vacancies is small, it does not affect the
bandgap. Then the vacancy level will continue to move up when
the concentration increases. By the time the vacancy level gets con-
tact with the top edge of the VB, the hybridization between them
will make the VB top widen, reducing the bandgap. Zhang et al.
[33] obtained WO3 with a high concentration of oxygen vacancies
through two-step synthesis, and the obtained dark blue powder not
only can absorb visible light but also exhibits better absorption per-
formance in the near-infrared region. The Tauc calculation results
show that the forbidden bandwidth of WO3 is reduced from the
original 2.61 eV to 2.09 eV. Then Zhang et al. used the synchrotron
radiation photoelectron spectroscopy to determine the Fermi level
and valence band top position of pristine WO3 and WO3–x . The
PDOS model is calculated under the first principle, and the energy
band structure diagram is obtained. After the introduction of oxy-
gen vacancies, unpaired W atoms provide electrons to the O atoms,
causing a broadening of the top of the VB. At the same time, the
PDOS model also shows a new energy level.
Chen et al. [34] produced surface disordered black TiO2 by
hydrogenation for the photohydrolysis of water to hydrogen. Li
3
Fig. 2. Oxygen vacancies causing the valence band top broadening up. Reprinted
with permission from Ref. [29]. Copyright 2012, American Chemical Society.
et al. [35] used a method of introducing the donor vacancy into the
anatase TiO2 by doping with sub-10 nm rutile TiO2 . After Valence-
band XPS detection and reference to Fermi calibration, the DFT of
the (110) plane of rutile TiO2 was calculated and the valence band
value was reduced from 2.89 eV to 2.60 eV. Naldoni et al. [29] syn-
thesized a black-shell TiO2 with a reduced bandgap structure. An
amorphous TiO2 precursor having a relatively high specific sur-
face area is used, and after heating in oxygen, hydrogenation is
carried out in H2 to obtain a black TiO2 having the surface disor-
der and internal vacancy. The diffuse reflectance UV–vis spectrum
shows the change of bandgap structure. The black TiO2 starts to
absorb the UV light at about 2.75 eV. Synchronous X-ray powder
diffraction results show that white TiO2 is completely anatase crys-
tal, while hydrogenated black TiO2 has 19% rutile phase and 81%
anatase phase. This is because annealing under a reducing atmo-
sphere produces point vacancy and the lattice structure of TiO2 is
changed. The H2 molecules with high temperature create oxygen
vacancies in the TiO2 matrix, and accelerate rearrangement. This
result indicates that the hydrogenation to obtain oxygen vacancies
or the self-doping by rutile TiO2 results in the same introduction
of the donor level. Both of these methods form doping of Ti3+ ,
which causes the valence band top to expand upwards, reducing
the bandgap width of TiO2 , as shown in Fig. 2.
2.3. Conductivity
The improvement mechanism of the conductivity of semicon-
ductor materials can be divided into two aspects: the introduction
of oxygen vacancies increases the carrier concentration inside the
material [36], and the presence of oxygen vacancies accelerates the
carrier transport rate [37–40].
For instance, Zheng [41] introduced oxygen vacancies on the
WO3 film by ion implantation with Ar+ at room temperature. The
higher the ion implantation concentration, the higher the oxygen
vacancies concentration. The samples after ion implantation were
named WO3 -1 × 1015 and WO3 -1 × 1016 , respectively. The experi-
mental results show that the resistance value of the WO3 material
containing oxygen vacancies is reduced by four orders of magni-
tude.
After introducing high concentration of oxygen vacancies into
the two-dimensional gas at the Al2 O3 /SrTiO3 interface, Lee et al.
[42] found that the interface showed metal conductivity, while
when the interface did not contain oxygen vacancies, it had no
metal conductivity. They believe that the oxygen vacancies in the
interface becomes an electron trapping site, aggregates a great
number of electrons, thereby obtaining metal conductivity. To
make further studies of the excellent property of black TiO2 , Lu et al.
[43] attempted to materials with structures and functions very sim-
ilar to those of B–TiO2 . They synthesized a TiO2 homojunction film
4 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
Fig. 3. Different concentrations of oxygen vacancies of semiconductor materials
appear in different colors. Adapted with permission from Ref. [48]. Copyright 2019,
Elsevier.
and found that the existence of oxygen vacancies reconstructed the
electronic interface, and the amorphous crystal structure realized
the metal conduction, thereby increasing the conduction velocity of
the carriers. Thereby, the conductivity of black TiO2 is enhanced to
have excellent photoelectric properties. In addition, different con-
centrations of oxygen vacancies will affect the conductivity of the
material to varying degrees. Manthiram et al. [44] prepared WO3–␦
with different “␦”. They found that the photoelectric properties of
WO3–␦ are determined by the local electrons of the polaron. When
␦ < 0.1, WO3–␦ exhibits semiconductor conductivity characteristics.
When ␦ > 0.1, WO3–␦ exhibits metallic conduction characteristics.
However, this increase has an upper limit. When ␦ is increased to
0.28, WO3–␦ will restore the semiconductor conductivity. Shahraki
et al. [45] used molecular dynamics simulation to study how the
different concentrations of oxygen vacancies affect the ionic con-
ductivity of BaTiO3 (BTO) nanowires. The results show that BTO
with highly concentrated oxygen vacancies has better conductiv-
ity than pristine BTO, which is about ten times. Lian et al. [46]
constructed 300 nm thick metal films of different materials on the
single-crystal LiNbO3 , and studied the influence of annealing on the
surface conductivity in different atmospheres, temperatures and
holding temperatures. The results show that the sample annealed
in 3% H2 + Ar for 6 h at 400 ◦ C is rich in oxygen vacancies, and the
conductivity is significantly enhanced.
2.4. Optical absorption spectrum
When oxygen vacancies are introduced into the material, the
color changes significantly. The color changes from shallow to deep,
and the higher the concentration of oxygen vacancies, the deeper
the color of the material. The absorption phenomenon of oxy-
gen vacancies is essential for the transition of electrons inside the
material which are excited after absorbing photon energy [47]. As
described in 2.1, the introduction of oxygen vacancies will cause
the valence band top broadening to move up, making the bandgap
narrower. Then less energy will be required for electronic transi-
tions, so the material has a wider range of light absorption, which
is reflected in the macroscopic change of the material color. For
example, the stoichiometric anatase TiO2 is macroscopically white.
Chen et al. [31] deduced black TiO2 powder after introducing oxy-
gen vacancies into TiO2 ; Yang et al. [48] annealed BiOIO3 in an
atmosphere of reducing gas and found that as the concentration of
oxygen vacancies increased, the bandgap width became narrower
and the powder gradually changed from white to yellow (Fig. 3). Ou
et al. [49] introduced oxygen vacancies in a series of metal oxides
by arc melting, and the color of the samples all showed the dark
transformation. Wang et al. [30] prepared TiO2 nanowire arrays
with low to high concentration of oxygen vacancies s. The results
show that the concentration of oxygen vacancies increases contin-
uously when the annealing temperature increases and the color
also change during this process.
The introduction of oxygen vacancies can also change the
surface reactivity of the material showing consequences on
adsorption–desorption phenomena.
2.5. Adsorption and surface reactivity
Adsorption activity is critical for applications of gas sensors. The
free charge carriers can participate at the level of the bonds at the
surface of the crystal with a gas adsorbed on it. Indeed, the with-
drawal or donation of charge carriers to the adsorbed gases change
the reactivity of the species adsorbed. When the gas molecules are
activated, they can react with another molecule of the gas mixture.
Conversely, the withdrawal or donation by adsorbed gas molecules
to the materials will change the charge carrier density, and thus
vary the conductivity. Simply measuring the conductivity of the
semiconductor sensing layers realizes the detection of the target
gases, which is the basic principle for the semiconductor gas sensors
described in this text.
Impurities on the surface of semiconductor materials may
induce a change in charge carrier concentration. These impurities
act the same as “dopants”. According to the “electronic” models,
the chemisorbed atoms or molecules can introduce discrete energy
levels on the surface of the semiconductor. The presence of these
energy levels will influence the density of carriers near the surface.
Volkenstein introduced the concept of ‘weak’ and ‘strong’ bonds
in chemisorption [50]. Thus, during the adsorption of a molecule on
a semiconductor, two types of adsorption are to consider:
• The weak chemisorption: the adsorbed molecule is electrically
neutral and the bond with the solid is carried out at the level of
the adsorption site without the participation of an electron or a
free hole of the crystal;
• The strong chemisorption: an electron or hole of the crystal is
involved in the bond. In this case, there are still different types
depending on whether the link formed is purely ionic (ionosorp-
tion), purely homopolar, or more generally an intermediate form.
The adsorption of a gas on the surface can introduce an electric
charge on the surface, complicating the situation. Indeed, when
a charge transfers between the adsorbed gas and the solid, the
molecule is ionized; the solid will take a charge of opposite sign
and a phenomenon similar to that of the electrochemical double
layer will appear. This double layer operates as an additional bar-
rier that has the effect of curving, the energy bands in the same
way.
Thus, in the case of adsorption of electron acceptors, a posi-
tive layer develops in the solid in the vicinity of the surface. These
charges create a potential barrier that increases the thermoelectric
work function T of an electron; while the adsorption stops when
T becomes close to the electronic affinity of the acceptor. The same
goes for a donor. In this case, ionization energy is used instead of
electronic affinity.
This band bending will have consequences for transfer charges
between the solid and the surface because a supplemental addi-
tional energy barrier eVs appears that plays an important role in
the transfer kinetics and adsorption equilibria.
The Fermi level will play a big role in the adsorption capacity
(quantity adsorbed per unit area). Indeed, one can show that the
adsorption capacity for acceptors decreases as the Fermi level is
lowered, while that of donors increases. This suggests that a p-type
semiconductor will absorb preferentially donors, and vice versa. It
also suggests that n-type sensors should be preferable as sensors
for acceptor gases.
 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
The band bending depends on the coverage of the surface and it
is clear that the adsorption heat and adsorption activation energy
evolve at the same time as the recovery rate, which invalidates
the simple Langmuir isotherm. Taking into account these charge
transfer phenomena, Volkenstein defined a more general isotherm
where one level of surface energy is involved. His expression for a
donor level is given by the following relationship:
ˇp
 (p) =
ˇp + 1
   −1
0 − EF − EC
ˇ=b f 1+ exp
20 kT
with:
b, the adsorption constant of the gas (at 0 coverage);
f0 , occupation probability of the chemisorbed states (according
to Fermi-Dirac distribution);
k, Boltzmann’s constant;
0 and -, typical phonon frequencies (in the range of
1011 –1013 Hz)
In Volkenstein’s isotherm, the adsorption capacity of a surface
depends not only on pressure and temperature, but also on the
electronic state of the system. It should be noted that Ec depends
on the amount of gas adsorbed since Ec = Ec0 + eVs . Vs , the surface
potential depends on the coverage, on the geometry of the solid
and eventually the presence of surface defects.
The use of this isotherm for real surfaces is complicated by the
presence of surface levels related to the defects, defects that are
usually not known or not well controlled.
These adsorption processes, of course, change the conductivity
of the surface, and this effect is used for the detection of gases. The
link between the conductivity of the semiconductor and the partial
pressure of the adsorbate gas is not always simple.
The problem is getting more complicated with a mixture of
gases. A set of competitions will be established, not only between
the initially adsorbed molecules and the gas molecules, but also
between gas molecules for free sites.
These competitions, which are at present poorly known, are one
of the major problems in gas detection. Indeed, it could be that,
in some cases, the molecules on the surface of the material and
strongly chemisorbed and prevent the gas you want to detect to
adsorb. There is a competition effect.
It often happens that a molecule, approaching the surface
directly reacts with the adsorbed species, leaving behind a blank
site. This phenomenon is exploited in the detection of combustible
gases by metal oxides. For instance, with SnO2 , CO is detected by
its reaction with the adsorbed oxygen.
Oxygen vacancy can effectively reduce the forbidden bandwidth
of metal oxide semiconductor materials and increase the number
of available charge carriers. After the introduction of oxygen vacan-
cies, the originally stable lattice structure will enter the metastable
state, thereby increasing the adsorption activity of the material,
oxygen vacancies at the surface act as adsorption sites [51–53] and
so the reactivity of the surface is enhanced by their presence.
For instance, Sun et al. [54] constructed an ideal model for ultra-
thin CeO2 nanosheets with highly concentrated oxygen vacancies.
Due to the presence of oxygen vacancies, many Ce atoms exhibit
an unsaturated coordination state and a valence state change, and
a five-coordinated Ce atom appears on the surface of the film,
which gives it better adsorption activity. In addition, the structure
of lattice changes, and the surrounding electronic structure changes
accordingly, making the unsaturated coordination metal atom at
the vacancy becomes the center of aggregation of the electrons,
thereby greatly increasing the carrier density at the vacancy. The
vacancy provides a new channel for the electron to transfer from
the inside of the material to the gas molecule, thereby improving
5
the adsorption activity of the surface of the material. For exam-
ple, Pei et al. [55] introduced oxygen vacancies in the {001} crystal
plane of TiO2 . Since O2 is only adsorbed at a position where an
excessive negative charge of the O Ti bond can be formed, O2 first
selectively adsorbs the oxygen vacancies to obtain higher adsorp-
tion energy. Thus, O2 is transformed from a physically adsorbed
state to a chemisorbed state, and the chemically adsorbed O2 traps
free electrons at the oxygen vacancies to form superoxide radicals,
(1) thereby accelerating carrier generation and transfer.
Sun et al. [56] introduced oxygen vacancies on atomic thickness
Co3 O4 nanosheets and enriched a large amount of uncoordinated
(2) Co3+ . This uncoordinated Co3+ forms much more active sites, which
enhanced the adsorption activity of Co3 O4 . What’s more, the intro-
duction of oxygen vacancies on ultra-thin nanomaterials causes
surface hybridization, increasing the density of states near the
Fermi level significantly, thereby accelerating the carrier transport
rate. Shen et al. [57] controlled the morphology of, so that the unsat-
urated coordination Co3+ ions accumulate more on the surface of
Co3 O4 bulk, changing the charge accumulation and distribution on
the surface and reducing the activation energy of the reaction. As
an adsorption center, Co3+ atoms can more efficiently achieve the
adsorption of O2 and complete the oxidation of CO2 more quickly.
The prepared Co3 O4 material can realize the surface adsorption oxi-
dation of CO at −77 ◦ C, the problem that the humidity of the gas
at room temperature affects the adsorption oxidation and cannot
be continuously reacted is solved. If oxygen vacancies are intro-
duced in different crystal faces of the material, different adsorption
results and reaction processes are generated due to different elec-
tronic structures at different positions. Zhao et al. [58] proposed
that BiOCl has oxygen activation characteristics under ultraviolet
light irradiation, but a single electron transfer process will take on
the (100) crystal plane of BiOCl and will reduce O2 to O2− , while the
(010) crystal plane will reduce O2 to O2 2− by means of two-electron
transfer. Li et al. [59] also found that when oxygen vacancies are
introduced into the (100) and (010) planes of BiOCl, the adsorption
mode and reaction path of the material for N2 are also different.
Theoretical simulations also show that oxygen vacancies pro-
vide an effective active site for oxidizing gases and enhance
adsorption performance [60]. An et al. [61] calculated the relation-
ship between the gas sensitivity and the concentration of oxygen
vacancies using DFT simulation. Then they found that the intro-
duction of oxygen vacancies in ZnO reduces the adsorption energy
of NO2 , accelerates the migration of carriers, shortens the bonding
length, and improves its gas sensitivity.
3. Ways to introduce oxygen vacancy
The preparation of oxygen vacancies can be divided into two
categories: direct and indirect method. The preparation of oxygen
vacancies is directly introduced during material synthesis, or indi-
rectly introduced by a post-treatment of the synthesized materials.
3.1. Direct introduction
The bottom-up preparation method of oxygen vacancies refers
to adjusting the metal valence state and causing partial lattice
oxygen vacancy by controlling the relevant parameters (reac-
tion temperature, the reaction time, the type and proportion
of the precursor, etc.) of the synthesis process of the material,
thereby synthesizing the oxygen-vacancy riched metal oxide mate-
rials [62–65]. Wang et al. [66] prepared rGO/SnO2 composite
(SnO2 –rGO–OVs) containing oxygen vacancies. In the preparation
process, SnO2 –rGO was first prepared by hydrothermal synthesis,
and then SnO2 nanoparticles are composited on the synthesized
substrate by chemical precipitation. By controlling the concen-
6 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026

tration of SnCl4 in the second step of chemical precipitation, the circuit supplies electrons to the inside of the material to trans-
concentrations of oxygen vacancies can also be different in the form W6+ into W5+ , in order to maintain charge balance, H+ in
SnO2 –rGO–OVs. The resulting material also has different degrees the electrolyte will combine with WO3 to generate Hx WO3 , Sub-
of improvement in gas sensitivity of ppb level NO2 . sequent low-temperature heat treatment removes H, and WO3–x
Zhou et al. [67] prepared high specific surface area indium tin with highly concentrated oxygen vacancies is obtained. It is the
oxide nanotubes (ITO NTs) by single nozzle electrospinning, and following formula:
gained samples with different concentrations of oxygen vacancies.
WO3 + xH+ + xe− → Hx WO3 (3)
The experimental results show that when the doping amount of
Sn is gradually increased from 3 mol% to 7 mol%, the performance Hx WO3 → WO3–0.5x + 0.5xH2 O (4)
of the sensor is improved. When the doping amount is further
In addition, oxygen vacancies can also be formed by breaking
increased, the performance of the sensor begins to decline. Com-
the original charge balance by doping metal elements. Deepa et al.
bined with the SEM results, the reason for the performance decline
[73]doped Zn in SnO2 to form a new Sn2+ state, and more oxygen
is because of the decrease of specific surface area of ITO NTs.
vacancies were generated for charge compensation.
Abd elmadjid et al. [68] used a solid-state reaction method
to prepare PbTiO3–␦ . The weighed PbO and Ti3 O5 powders were
3) High-temperature reduction method
mixed uniformly and pressed into pellets, followed by calci-
nation at high temperature, and the concentration of oxygen
The elements in the material will have different degrees of
vacancies was controlled by controlling the calcination tempera-
volatilization in the form of gases, ions and atoms in the molten
ture.
state. The evaporation rate of O element is generally much faster
than that of metal atoms. Therefore, the O element of the mate-
3.2. Indirect introduction
rial in the molten state will be lower than the stoichiometric
ratio. After rapid cooling, the material still maintains this unbal-
The secondary treatment based on the pristine metal oxides that
anced stoichiometric ratio, thereby forming oxygen vacancies. The
have been synthesized to introduce oxygen vacancies is currently
high-temperature reduction method is to treat the semiconduc-
widely used. This method uses various methods to reduce the syn-
tor material at a high temperature, high pressure in an inert
thesized materials, so that the original stoichiometric oxides lose
atmosphere to generate oxygen vacancies. And the higher the tem-
oxygen atoms, thereby generating oxygen vacancies. According to
perature is in a reductive atmosphere, the more oxygen vacancies
the different ways of reduction, the methods can be classified into
will be created. Commonly used reducing agents are H2 , Al, Mg, etc.
the following five categories:
Among them, H2 is the most efficient reducing agent [74]. Chen
et al. [34] produced black TiO2 by high-temperature hydrogena-
1) Chemical reduction method
tion. There are also a large number of studies that introduce oxygen
vacancies into materials by annealing in a reducing atmosphere
The chemical reagent reduction method is a relatively com-
[75,76].
mon method for introducing oxygen vacancies. Through the strong
reducibility of chemical reagents, the metal ions originally in the
4) High energy beam reduction method
high valence state are reduced to a low valence state, resulting in
an imbalance of the internal stoichiometric ratio of the material,
When oxygen vacancies need to be introduced into coatings or
thereby forming oxygen vacancies [69]. To enhance the photoelec-
films, the application of a high-energy beam as a heat source can
trochemical performance of BaSnO3 (BSO), Kim et al. [70] prepared
achieve rapid heating and cooling of the coating or film without
a stoichiometric BSO through the sol–gel method, then soaked in
affecting the matrix material. At present, using a high-energy beam
NaBH4 solution for three hours at room temperature, and obtained
to strengthen the surface of the material to obtain higher surface
samples with different concentrations of oxygen vacancies as 2.8%,
hardness or wear resistance is a research hotspot in the field of
6.1%, 8.7%, 12.1% and 17.2% by adjusting the concentration of NaBH4
materials science. The use of a high-energy beam to improve the
solution.
functionalization of materials also has broad prospects. Ou et al.
[49] used an arc melting method to introduce oxygen vacancies
2) Electrochemical reduction method
into metal oxides. The results show that the arc melting method
can effectively narrow the bandgap of ZnO, Cu2 O, ZrO2 , In2 O3 , Y2 O3
The electrochemical reduction method is to apply a certain
and SnO2 .
voltage across the material through an external circuit to provide
The laser is a high-energy beam that is currently used more, and
electrons inside the material to break the internal balance of the
its pulse width is short, which can generate extremely high energy
material and form oxygen vacancies. Li et al. [71] prepared TiO2
in a short time. The laser etching method [77,78] can generate
with highly concentrated oxygen vacancies by the electrochemi-
extreme high temperature and high-pressure environments locally
cal method. They fabricated the TiO2 nanotube arrays (TiO2 NTAs)
in the metal oxide material, and after the etching is finished, a large
through anodization method firstly, and then anneal the TiO2 NTAs
number of oxygen vacancies will be formed due to rapid heating
to crystallize it. After the annealed sample was activated under the
and cooling. The plasma is another typical high-energy beam. It
synthesis conditions, the electrochemical reduction was carried out
has a very high activity and easily reacts with atoms on the surface
by placing the sample as a cathode in a 0.27 wt.% NH4 F ethylene
of the material [79,80]. Xu et al. [81] used Ar plasma engraving to
glycol solution to obtain black TiO2 nanotube arrays with oxygen
treat Co3 O4 nanosheets. XPS result proved it is an effective way
vacancies.
to fabricate Co3 O4 nanosheets with highly concentrated oxygen
Wang et al. [72] used the three-electrode method to electro-
vacancies. Wang et al. [82] used H2 plasma to treat TiO2 . Compared
chemically reduce WO3 , using H2 SO4 as the electrolyte. The color
with Ar plasma, H2 plasma not only has high activity, but also has
of WO3 changed from bright yellow to blue as the experiment pro-
strong reducibility and can obtain a higher concentration of oxygen
gressed, XPS results indicate that oxygen vacancies are generated
vacancies.
inside the material. Wang et al. proposed that since the external
 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
Fig. 4. Detection circuit of a metal oxide semiconductor sensor.
Fig. 5. Working mechanism for metal oxide semiconductors.
5) Thermal spraying method
The preparation of metal oxide semiconductor coatings with
highly concentrated oxygen vacancies by atmospheric plasma
spraying (APS) is a promising method. The plasma flame flow of APS
is generated by H2 ionization. The plasma flame flow in the spraying
process has extremely high temperature, extremely high plasma
activity, and H2 plasma has extremely strong reducibility. These
three characteristics make this preparation method easy to obtain
a high concentration of oxygen vacancies. The solution precursor
plasma spraying (SPPS) can combine the advantages of chemical
synthesis, high-energy beam reduction and plasma treatment. The
preparation process of the required raw materials is simple, and it
is easier to control the number of oxygen vacancies, the prepara-
tion method is simpler and more direct, and it is a highly efficient
preparation method of materials with rich oxygen vacancies.
4. Applications in gas sensing materials
As explained before, metal oxides are good materials for prepar-
ing gas sensors. The general working principle is the following:
when exposed to a specific gas, the resistance of gas-sensitive mate-
rials will change [83,84]. Indeed when the gas is adsorbed on the
surface and if the interaction is strong enough (chemical adsorp-
tion), electrons can be exchanged between the adsorbed molecules
and the semiconductor which leads to a change of the concentration
of charge carriers and as a consequence, the conductivity (Fig. 4)
[83].
The amount of adsorbed gas molecules depends on the concen-
tration of the target gas, so the relationship between the target gas
concentration and the resistance value is established.
The working mechanism of metal oxide semiconductors is
shown in Fig. 5 [85,86]. Taking n-type semiconductors as an
example, when in air, the oxygen molecule will form O2− , O-
7
or O2 - according to the temperature after the absorption, form-
ing a depletion layer, an increase in potential barriers, and an
increase in resistance. Reducing gas, such as CO, H2 , etc. will react
with the O ions, release electrons, increase the carrier concen-
tration, reduce the potential barrier, and reduce the resistance.
When in contact with oxidizing gases, the situation is exactly the
opposite.
The introduction of oxygen vacancies in semiconductor materi-
als can effectively improve gas-sensitive performance, especially
for sensitivity. Wang et al. [87] used a post-oil bath annealing
method to prepare a Ce-doped ␣-Fe2 O3 acetone sensor FeCe10
(Fe/Ce = 10). Ce4+ captured the lattice oxygen of ␣-Fe2 O3 to form
Ce3+ , thereby forming oxygen vacancies. XPS results show that after
doping, the peak area of the vacancy oxygen in O 1s increases, that
is, the concentration of oxygen vacancies increases. The EPR results
show that the resonance curve appears at a magnetic field strength
of 3525G, which proves that the oxygen vacancies contains a large
number of free electrons, so that the carrier concentration at the
oxygen vacancies increases to become the adsorption center and
enhances the adsorption performance of the material. Gas sensing
results show that FeCe10 shows the best performance at 220◦ C,
which is much lower than pristine ␣-Fe2 O3 (280 ◦ C), and the sen-
sitivity of FeCe10 is higher than that of pristine ␣-Fe2 O3 by 1.3–2
times at 220 ◦ C. Lu et al. [88] prepared WO3 by a facile one-pot
microwave-assisted hydrothermal method and studied their gas-
sensitive response to acetone. XPS results indicate the presence of
oxygen vacancies. The optimum operating temperature of the SnO2
microspheres for 100 ppm acetone vapor is 320 ◦ C, the response
value can reach 31. Compared with other WO3 -based ethanol sen-
sors, WO3 containing oxygen vacancies have better overall gas
sensitivity.
Peng et al. [89] used a simple one-step autocatalytic process
of industrial ZnFe2 O4 (C-ZFO) and tartaric acid (TA) to prepare
ZnFe2 O4 -based acetone sensor. During the synthesis, the molar
ratio of TA to C-ZFO was controlled to be 5:1 and 10:1, respec-
tively, and ZFOV1 and ZFOV2 were obtained. The XPS results showed
that the concentration of oxygen vacancies of C-ZFO was 24.83%.
The concentration of oxygen vacancies of ZFOV1 after autocatalytic
reaction with TA was 27.92%, and the concentration of oxygen
vacancies of ZFOV2 with a higher concentration of TA reached
40.22%. The gas testing results show that the optimal temperature
of the three materials is 280 ◦ C. At this temperature and 600 ppm
acetone, C-ZFO has a response of 16, while the response of ZFOV1 is
36 and the response of ZFOV2 is 70, as shown in Fig. 6.
To heat the sensing materials at relatively high temperatures for
a long time involves problems such as: substrates able to sustain
high temperatures, stability of the materials, hot spot and power
consumption. Also, to avoid heating, light can be used as an energy
source and these last years a lot of studies about light assisted metal
oxide sensors were published. The idea is to excite the electrons
8 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
Fig. 6. Responses to 2.5 –600 ppm acetone at 280 ◦ C. Adapted with permission from
Ref. [89]. Copyright 2019, Elsevier.
and force photoadsorption (photodesorption) at the surface of the
metal oxide.
For this application, the performance of the sensor is related to
its ability to absorb the light. One strategy is to use an absorbing
phase, a dye for instance [90] like what is done for Dye-Sensitized
Solar Cells (DSSC) or Grätzel cells [91], or the extent of the optical
absorption range to lower wavelengths. For the latter, the creation
Fig. 7. Preparation of ZnO1– x coating by SPPS and characterization of oxygen vacancies. Adapted with permission from Ref. [93]. Copyright 2017, Elsevier.
of high concentrations of oxygen vacancies is a good way to achieve
the goal.
Geng et al. [92] prepared a ZnO coating by suspension flame
spraying (SFS) and tested the gas sensitivity of NO2 . SFS has a
high flame flow temperature and a fast cooling rate. This high-
temperature/rapid cooling method can fabricate coatings with
highly concentrated oxygen vacancies effectively, and the oxy-
gen vacancies concentration increases as the spraying distance
increases. Geng et al. used spray distances of 275 mm and 325 mm,
respectively, and named the samples D275 and D325, respectively.
Photoluminescence spectra results showed that compared with the
ZnO powder before spraying, the D275 at the wavelength of 375 nm
was weakened, while the deep-level emission of D275 in the vis-
ible region was significantly enhanced. The D325 changes more,
its near-band-edge emission almost disappears, and the deep-
level emission is greatly enhanced compared with D275. The XPS
results show that the unsprayed ZnO powder has an concentra-
tion of oxygen vacancies of about 0.2%, and the D275 and D325
have an oxygen vacancy concentration of 1.9% and 3.2%, respec-
tively. The bandgaps of unsprayed ZnO powder, D275 and D325
were 3.32 eV, 3.01 eV and 2.78 eV, respectively, by Tauc calcula-
tion. The gas sensitivity test of 0.25–1.0 ppm NO2 under visible
light conditions, D275 and D325 both showed better gas sensitivity,
and the gas sensitivity of D325 was better than D275. Zhang et al.
[93] also used precursor solution plasma spraying (SPPS) to prepare
ZnO1–x coatings (Fig. 7a). Compared with SFS, SPPS not only has a
higher temperature (>10,000 ◦ C) and faster cooling rate (>105 K/s),
 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
but also the plasma generated by H2 has strong reducibility and
is more likely to obtain high oxygen vacancy concentration. The
calculated ZnO1–x oxygen vacancy concentration reached 86.84%
by XPS results (Fig. 7b). The EPR results showed that resonance
peaks appeared at g≈1.9610 and g≈2.0034 (Fig. 7c). The bandgap
of the ZnO1–x coating prepared by SPPS is about 2.15 eV by Tauc
calculation. These results indicate that fabricating coatings through
thermal spraying method can improve the gas-sensitive properties
of metal oxide semiconductors.
Zeng et al. [94] used NaBH4 as a reducing agent to incorpo-
rate a high concentration of oxygen vacancies in SnO2 , and coated
the obtained SnO2 on an alumina substrate to make a sensor. The
response to 300 ppm ethanol at 190 ◦ C of the obtained sensor can
reach 120.3, which is much higher than the pristine SnO2 sensor.
This is because the presence of oxygen vacancies enhances the
adsorption of oxygen molecules and thus increases the active site.
Ma et al. [95] prepared nano-spindle like In2 O3 with abundant oxy-
gen vacancies through solvothermal method. Sensors made from
this material have excellent selectivity for methanol. The response
value to 100 ppm of methanol at 240 ◦ C was 27. The most notice-
able performance of this sensor is its extremely short response and
recovery time. The response time is less than 1 s and the recovery
time is 10 s. There are two main reasons for its excellent gas-
sensitive properties: first, the material’s special layered structure
makes it have a very large specific surface area; second, the intro-
duction of oxygen vacancies. The presence of oxygen vacancies
increases the active sites on the surface of the material, thereby
enhancing the adsorption performance. At the same time, oxygen
vacancies make the depletion layer wider and provide more chan-
nels for electronic exchange. Zaki et al. [96] investigated the role of
oxygen vacancies in enhancing the room temperature gas sensitiv-
ity of VO2 to CO2 . The research results are the same as the first two,
that is, the introduction of oxygen vacancies increases the active
sites on the surface of the material and enhances the adsorption
performance.
Xu et al. studied the SnO2 thin film triethylamine sensor and
used various methods to improve the sensor performance. When
they are modified with platinum single atoms, this Pt / SnO2 sensor
has excellent performance, its response to 10 ppm triethylamine at
200 ◦ C is 136.2, the minimum detection limit is 7 ppb [97]. After
they introduced oxygen vacancies on the SnO2 film by annealing,
this oxygen vacancy-rich SnO2 sensor also has excellent perfor-
mance. Its response to 10 ppm triethylamine at room temperature
can reach 150.6, and has a very short response and recovery speed
[98]. It can be seen from this that the introduction of oxygen vacan-
cies will greatly enhance the gas sensing performance of the sensor
at room temperature.
Designing special microstructures, such as hollow spherical
shell structures, can not only expands the specific surface area, but
also forms optical traps that enhance the light-absorbing ability
and light utilization efficiency of the material. Therefore, combin-
ing oxygen vacancies with special microtopography can further
enhance the performance of semiconductor materials [99].
In addition, combining oxygen vacancies with heterojunctions
can also further enhance the gas sensing properties of the materials
[100].
5. Conclusions and prospects
Metal oxides with highly concentrated oxygen vacancies can be
useful for the application of gas sensors. The introduction of oxy-
gen vacancies can effectively reduce the forbidden bandwidth of
wide-bandgap semiconductors, and improve the semiconductor’s
adsorption activity and light absorption performance. Although
the current oxygen vacancies preparation method is effective and
9
achieves an improvement in material properties, it is often rela-
tively complicated and costly, and is not convenient for large-scale
commercial applications. The hydrothermal synthesis mentioned
in the review paper is only suitable for the laboratory environ-
ment, since its production is low, the cost is high, and it is difficult
to convert into industrial production. Similarly, the method of
synthesizing materials and then reducing them is also slightly com-
plicated, which makes it difficult to control the cost and improve
production efficiency. Therefore, the research and development of
high efficiency and low-cost method for preparing materials with
oxygen vacancies are one of the research focuses on semiconduc-
tors with highly concentrated oxygen vacancies. Future research is
also needed on the stability of oxygen vacancies. The biggest chal-
lenge of metal oxide semiconductors with oxygen vacancies is the
oxidation of the materials. For example, in a high-temperature aer-
obic environment, oxygen vacancies on the surface of the material
is easily oxidized, resulting in a decrease in the concentration of
oxygen vacancies of the material. It is necessary to study how to
prevent oxygen vacancy from being oxidized in a high-temperature
aerobic environment, then increase the serviceability of metal
oxide semiconductors in harsh conditions. In the context of the
Internet of Things, wearable is the development trend of sensors.
How to prepare flexible metal oxide semiconductors rich in oxy-
gen vacancies is another challenge for this material in the future.
Besides, reducing the power consumption of the sensor and reduc-
ing the heat of the components are also problems that need to be
solved in the future.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work is supported by the National Key Research and Devel-
opment Program of China under Grant No. 2017YFE0115900, the
Natural Science Foundation of China under Grant No. 51872254 and
the Yangzhou City-Yangzhou University Cooperation Foundation
under Grant No. YZU201801.
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Biographies
Chao Zhang received a B.E. degree from the Chongqing
University (China) in 2003 and a joint Ph.D. degree from
Technology University of Belfort-Montbéliard (France)
and Xi’an Jiaotong University (China) in June 2008.
From September 2007 to January 2009, he worked as a
teaching-research assistant in Technology University of
Belfort-Montbéliard. Since Feb 2009, he is a postdoctoral
researcher, and then a senior researcher in Materials Sci-
ence Department of Engineering School of University of
Mons (Belgium). In 2014, he joined Yangzhou University
(China) as professor where he is leading a research group.
Since 2016, he is Vice Dean of College of Mechanical Engi-
neering. His research interests include thermal-sprayed
techniques and coatings, especially gas sensing and wear-resistant coatings.
Guifang Liu received his B.S. degree in 2017 at Hefei Uni-
versity of Technology. He is currently pursuing his M.S.
degree at Yangzhou University. He takes interests in sens-
ing materials for gas sensors.
Xin Geng received his B.S. degree in 2013 at Yangzhou
University (China), his joint Ph.D. degree at University of
Mons (Belgium) and Yangzhou University. He is currently
a postdoc researcher at Wayne State University (USA) and
takes an interest in smart materials for gas sensors.
12 C. Zhang, G. Liu, X. Geng et al. / Sensors and Actuators A 309 (2020) 112026
Kaidi Wu received his B.S. degree in 2017 at Anhui Univer-
sity of Science and Technology. He is currently pursuing
his PhD degree at Yangzhou University. He takes interests
in smart materials for gas sensors.
Marc Debliquy received his Ph.D. at Faculty of Engineering
in Mons (Belgium) in1999 in the field of organic semicon-
ductors for fire detection. He joined the Sochinor Company
in 2000. He left in 2003 for joining Materia Nova. He was
responsible for the research activities in the field of gas
sensors. Since October 2008, he joined the Material Sci-
ence Department of Faculty of Engineering of University
of Mons and worked as a team leader of semiconductor
and sensor group. He was promoted as associate profes-
sor in September 2013. His main research interest is smart
coatings for chemical detection. He is also co-founder of
the spin-off company B-Sens specialized in optical fiber
sensors.