Materials Science in Semiconductor Processing 156 (2023) 107271

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Materials Science in Semiconductor Processing

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

Gas sensing mechanisms in ABO3 perovskite materials at room

temperature: A review
Mahsa Souri , Hossein Salar Amoli *
Faculty of Chemistry, Amirkabir University of Technology, Tehran, Iran

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

Keywords: This article is a summary of the latest literature on gas sensing properties of perovskite materials at room
Gas sensing temperature. Among all types of sensors, the perovskite materials with a general stoichiometry of ABO3 have
Perovskite materials attracted extensive attention due to their ease of fabrication, high sensitivity, selectivity, and stability. However,
Mechanisms
high operating temperature is one of the limiting factors affecting the stability of the sensors. To resolve this
Room temperature
challenge, several researchers have focused on developing perovskite gas sensors operating at room tempera­
tures. In this review, room temperature perovskite gas sensors developed for detection of the various gases have
been reviewed. Further, the sensing mechanism and the influential factors on the performance (sensitivity,
selectivity, and stability) of the sensors have been discussed. In addition, the influence of the relative humidity,
dopant, and morphology on the sensing mechanism and selectivity have been highlighted. It is concluded that
dopants cause defects in ABO3 by creating oxygen vacancy and enhancing the gas sensing properties. Also, the
uniform distribution of the pores on surface morphology boosts sensitivity. Understanding the operational
mechanism is the heart of any sensor’s development. This paper provides support for research on solving the
problems related to perovskite gas sensing.

1. Introduction concentration of the charge carrier as well as changes in resistance.

Thus, sensing materials and their structures play a crucial role in sensing
In recent decades, with the fast urban-industrial growth, extreme air performance and in determining the selectivity plus sensitivity of sen­
pollution is widespread due to emissions from industrial sources, traffic, sors [9]. Among ternary oxides, perovskites with the general formula of
and transport vehicles. Human health is affected by air quality where ABO3 exhibit various physiochemical properties along with tunable
leakage of flammable and toxic gases threats human life [1]. Gas sensing electronic conductivity, making them advantageous compared to binary
technologies are imperative in our daily life not only due to enabling the metal oxides [10]. Several perovskite materials have been studied as gas
monitoring of air quality [2] and detecting toxic gases [3,4] and volatile sensors due to their stability [11]. Oxygen vacancies in the perovskite
organic compounds (VOCs) [5], but also they are practical in medical oxide structure are highly critical in gas sensing mechanisms [12]. The
diagnosis [6]. To achieve this objective, various gas sensors including perovskite structure, containing two differently-sized cations, can
calorimetric, potentiometric, catalytic, chemiresistive, and conducto­ accommodate a large number of dopants with different ionic radii,
metric have been studied [7]. A usual chemiresistive gas sensor includes which can change charge carrier concentration, and band gap width,
an active sensing material, with conductivity very sensitive to the sur­ and thus modify their properties without altering their crystal lattice
rounding environments. Recently, of all numerous chemiresistive sen­ [12–14].
sors, metal oxide semiconductors have been investigated extensively The sensing properties of chemiresistive sensors are affected by
given their ease of fabrication, low production cost, smooth operation, environmental conditions including humidity, operating temperature,
and the possibility of miniaturization [8]. The sensing mechanism of and gas concentration. The limit of detection, response/recovery times,
metal oxide gas sensors is based on the difference in resistance of the sensitivity, selectivity, drift, and reversibility are the key sensing pa­
sensing layer in the gas atmosphere and air. Adsorption and electron rameters. An ideal sensor has minimum response/recovery times while
transfer between the target gas and sensing layer lead to altered maximum sensitivity and selectivity. When the sensor cannot recover

* Corresponding author.
E-mail address: [email protected] (H. Salar Amoli).

https://doi.org/10.1016/j.mssp.2022.107271
Received 19 July 2022; Received in revised form 7 December 2022; Accepted 8 December 2022
Available online 12 December 2022
1369-8001/© 2022 Elsevier Ltd. All rights reserved.
M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

completely, drift will occur which is an indication of the irreversibility of target gases and chemisorbed oxygen molecules. The chemisorbed ox­
the sensor. Full recovery is another factor of an ideal sensor [15]. ygen molecules extract electrons from the surface layer which leads to
Operating temperatures are critical in conductivity, surface reaction the formation of the chemisorbed oxygen ion species such as O−2 , O− , and
kinetics, and electron transfer; thus, the operating temperature affects O2− at different ranges of operating temperature [32,33]. The detailed
gas sensing performance and eventually exhibits a significant effect on reactions are shown in Equations (1)–(4) [6]. The general sensing
the selectivity, sensitivity, and response/recovery time of the sensor. mechanism of the semiconductor is shown in Fig. 1. Due to the extrac­
Metal oxide-based sensors usually operate at a high temperature within tion of electrons by chemisorbed oxygen species, electron density de­
150–500 ◦ C, since sufficient thermal energy is required to overcome the creases whereby a resistive electron depletion layer and semiconductive
redox reaction’s activation energy barrier [16]. However, high oper­ core in n-type semiconductors are formed. Also, the adsorption of the
ating temperature limits their widespread application because of high oxygen ions on the surface of the p-type semiconductors forms a hole
energy waste, decreased sensor stability, and increased risk of explosion accumulation layer near the surface plus an insulating region at the core
in flammable as well as explosive gases [17,18]. In addition, the high of semiconductors [34]. In n-type semiconductors electrons are charge
temperature could alter the microstructure of sensing materials, result­ carriers, due to reduction in electron concentration, the conductivity
ing in a loss of performance [9]. Room temperature operating gas sen­ diminishes leading to increased resistance. Unlike n-type semi­
sors that do not require heaters are more energy-saving, cost-effective, conductors, in p-type semiconductors, holes (h.) are the main charge
safe, and portable [17]. Thus, an efficient and reliable gas sensor that carriers and decrease in electron concentrations causes an increase in
can work at room temperature is needed. As such, enormous efforts have holes’ concentration thus increasing conductivity and reducing the
been made to reduce the operating temperature [19]. resistance of the semiconductor [9,16]. The schematic of the receptor
On the other hand, there are still some challenges associated with and transduction functions of metal oxide gas sensors is shown in Fig. 2.
room temperature sensors. The sensing performance of this kind of
O2(gas) →O2(ads) Equation 1
sensor is limited and many of them show low sensitivity because of
inadequate active oxygen species at the surface due to large adsorption
O2(ads) + e− →O−2(ads) (T < 300◦ C) Equation 2
energy [20,21] with the response/recovery time being very long [9,22].
Further, relative humidity at room temperature operating sensors is a (
major interference. At this temperature, H2O molecules compete with O−2(ads) + e− →2O−(ads) 100◦ C < T < 300◦ C Equation 3
oxygen molecules for the surface adsorption leading to diminished
active oxygen species at surface of the sensing materials [1,23,24]. The O−(ads) + e− →O2−(ads) (T > 300◦ C) Equation 4
selectivity of the sensors can also be limited.
In this regard, some strategies have been developed such as opti­ When p-type perovskite interacts with a reducing gas (such as
mizing the nanostructure for enhancing the surface-to-volume ratio and ethanol, formaldehyde, methane, hydrogen sulfide, acetaldehyde,
modifying microstructures by tuning the crystallite size, morphology, acetone, etc.), the surface resistance increases. The reaction of the
and grain boundaries, along with the synthesis of hybrid and composites reducing gas with the adsorbed oxygen ions releases the electrons
nanomaterials [25], and light activation [26]. The grain size of a trapped by the oxygen ions and annihilates the holes (equation (5)); due
semiconductor gas sensor influences the sensing performance. Studies to the decrease in charge carrier concentration, the sensor resistance
have shown that when the grain size of the sensing materials is com­ grows [35].
parable to twice their Debye length, they reach the best performance h. + e− = null Equation 5
[16,19,27]. Illuminating the surface of perovskites and generally metal
oxide semiconductors can change the photocarrier concentrations and The interaction of the p-type perovskite with oxidizing gases such as
affect the surface electronic properties, leading to the activation of nitrogen dioxide, hydrogen peroxide, ozone, carbon dioxide, and sulfur
layers by light instead of heat [26,28]. In addition to perovskite resistive dioxide results in elevated holes’ concentration and reduced resistance
sensors, there are some new room temperature operating gas sensors [36].
such as optical perovskite sensors [29–31], though they are not mature The interaction of reducing gases with n-type perovskites that usu­
enough and we do not focus on them in this review. ally contain oxygen vacancy deficiency leads to higher electron con­
In 2015, Zhang et al. reviewed the fundamental research and ad­ centration and lower perovskite resistance [37]. The ionized
vances in room temperature operating sensors. They also clarified the chemisorbed oxygen species inject electrons into the semiconducting
sensing mechanism and application of nanomaterials [16]. In 2019, a core by oxidizing the reducing gases. On the other hand, in an oxidizing
summary of the most important developments in the perovskites gas environment, the perovskite resistance increases [38].
sensors including sensing mechanism and experimental strategies was The mechanism of the reaction of NO2 and NH3 gases on the surface
provided by Bulemo et al. [10]. of the Sr-doped BaTiO3 has been studied before [39]. The reaction of the
To the best of our knowledge, a review of room temperature oper­ NO2 with adsorbed O−2 at the surfaces of the samples was a single step
ating perovskite gas sensors by focusing on the mechanism is still (Fig. 3a), while for NH3 it was a two-step reaction (Fig. 3b), during
missing. Herein, for the first time, we intend to present an overview of which NH3 reacts with O−2 to form NO2 and H2O. Then, the reaction of
recent developments in perovskite gas sensors from the perspective of the NO2 with the atmospheric oxygen releases the free electrons back to
operating temperature. We discuss the successful strategies and mech­ the conduction bands of Sr-doped BaTiO3.
anisms in this area.
2.1. Humidity effect on sensing mechanism
2. The sensing mechanism of perovskite materials
The detection of the target gases under real conditions requires
The widely accepted gas sensing mechanism of the perovskite oxide operation in a humid atmosphere. One of the interferences in gas sensors
resistive sensors is based on changes in the conductivities of the active at room temperature is humidity. Almost all types of metal oxides tend
materials, resulting from the adsorption and desorption of gas molecules to adsorb moisture on their surfaces, which would affect their sensitivity
on the surface of sensing material after exposure to the target gas, with [40]. When the sensors are exposed to air, the absorbed oxygen species
the mechanism being influenced by the sensor materials and target and moisture react and form hydroxyl groups (OH− ) (Equation (6)),
gases. When the semiconductor perovskites are surrounded by air, the which impede the reaction of the target gas with chemisorbed oxygen
oxygen molecules are absorbed on the surface of the semiconductor. The species. Thus, the decline in the response and increase in response/r­
common sensing mechanism consists of surface reactions between the ecovery times can be observed [41] as a consequence of the reduced

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M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

Fig. 1. a, b) The general gas sensing mechanism of semiconductors c) top view of sensor.

Fig. 2. Schematic illustration of receptor and transduction functions of metal oxide gas sensors in A) a n-type semiconductor and B) a p-type semiconductor in
presence of the reducing and oxidizing environment.

number of oxygen sites [23]. with the elevation of the RH level and formation of the single hydrogen
( ) bound water molecules increases proton demand and as a result, the
H2 O + O−(ads) O−2(ads) ↔ 2(OH − ) + (2)e− Equation 6 conductivity and capacitance grow. So, the fast response/recovery times
of the Ba0.75Sr0.25TiO3 when used for ammonia sensing at 30, 50, and
Investigating the effect of humidity on acetone sensing properties of
70% RH are attributed to the high mobility of H3O+ and OH− ions
the La1-xSrxCoO3 (x = 0, 0.1) revealed that greater responses were ob­
through condensed water in the pores of the sensing layer, where the
tained in dry air compared to wet air and about 1% change was observed
main interaction of the ammonia and water is based on proton exchange
with each 10% change in RH [42].
mechanism. Because of their ability to form hydrogen bonds, the water
On the other hand, A. Gurlo did not support this idea and clarified
molecules are replaced with NH3 molecules, as displayed in Fig. 4 [45].
that only physisorbed oxygen species exist at room temperature [43].
Li et al., in 2017 [37] indicated that the conductance of the Bi2WO6
According to previous studies [44], the physisorbed water layer formed
sensor increases in humidity, as a result, the ammonia sensing was

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 M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

Fig. 3. a) NO2 and b) NH3 sensing mechanism of Sr doped BaTiO3 NPs.

days, respectively at 50 and 90% RH [49]. Another study [50] on

acetone and NO2 sensing properties of thiocyanate-doped organometal
halide perovskite, CH3NH3PbI3-x(SCN− ), explored the effect of humidity
on the stability of the sensor. The results indicated that the stability after
7 days diminished in humid air by 11% for NO2 and 13% for NH3.
However, the stability dramatically dropped for the CH3NH3PbI3-based
sensor without doping and its response to 5 ppm NO2 fell significantly
(about 60%) after one day of exposure to humid air.
In 2017, Liu et al. [42] assessed the effect of humidity on the acetone
sensing performance of undoped LaCoO3 and La1-xSrxCoO3 nano­
particles at room temperature. They mentioned that acetone exhibited
the higher response in dry air. However, the variation in response rates
was small, despite significant changes in relative humidity, about 1% of
response: reduction per 10% change in relative humidity for La1-xSrx
CoO3 nanoparticles. The effect of humidity is related to the displacement
of the adsorbed oxygen species by water molecules leading to the
decreased response.
Recently, Tie et al. [41] reported that the Pr-doped BiFeO3 formal­
dehyde sensor suppressed the effect of humidity on the sensing perfor­
Fig. 4. Schematic indication of the ammonia-water interaction [45]. mance. Also, the response ratio of the sensor at 30% and 89% RH was
0.104 where the variation of the response/recovery times for the doped
sensor was lower in comparison with the undoped one. This is explained
affected by the physisorbed water molecules. In 2018 [46], they fabri­
by excellent reversible redox cycle properties of praseodymium
cated a humidity-independent ammonia gas sensor and used it for
(Pr3+/Pr4+ redox pairs) with the following equations explaining the
ammonia detection in the breath as a medical biomarker for stomach
reactions that occur on the sensor surface.
infections by Helicobacter pylori bacteria and kidney disorders. As the
humidity of the exhaled breath varies, the fabrication of the Pr3+ + 2(OH − ) → Pr4+ + H2 O + O−(ads) Equation 7
humidity-independent sensor is important. The researchers indicated
that coating the CuBr sensing layer with 100 nm thick inactive CeO2 Pr4+ + (e− )→Pr3+ Equation 8
eliminated the humidity dependence of the sensing layer at room tem­
perature. Instead of Cu2+, Ce4+ in CeO2 at the top layer would react with The represented redox cycle regenerates the adsorbed oxygen mol­
water molecules and eliminate the interaction of the moisture and ecules by eliminating excess electrons, and it can adsorb oxygen plus
sensing layer. It has been indicated that the CeO2 nanoparticles work as formaldehyde molecules. Also, at lower contents (5–25 ppm) of form­
hydroxyl group scavengers [47]. By exposing the Ce–In2O3 to humidity, aldehyde and humidity, strong hydrogen bonding between formalde­
hydrogen ions (H+) are generated with the reduction of Ce4+ to the hyde and hydroxyl groups would accelerate the surface reaction and
Ce3+, which scavenges the formed hydroxyl group from absorbed water shorten the response time (equation (9)).
molecules. OH − O−
HCHO → CHOO− + .OH→CO2 + H2 O Equation 9
In 2019, Casanova-Chafer et al. [48] investigated the gas sensing
properties of a graphene layer decorated with perovskite nanocrystals at
ambient temperature. The researchers showed that the fast-irreversible 3. Selectivity mechanism of the perovskite gas sensor
degradation of the CH3NH3PbI3 in humid atmospheres was mitigated by
the hydrophobic properties of the graphene base, and the variation of Considering the high sensing potential of the MOSs achieving se­
the sensitivity for NH3 and NO2 detection in the presence of humidity lective gas sensors are in high demand. However, selective detection is
decreased to less than 5%. still a challenge for researchers. The Selectivity of the gas sensor is the
In a study performed in 2020 on a hybrid methylammonium tin io­ ability of the sensing materials to identify the target gas in the inter­
dide (MASnI3) and tin dioxide (SnO2) sensor, it was shown that the ference gas mixture. There are some physical and chemical modification
stability of the NO2 sensor decreased from at least 30 days to 20 and 10 methods for improving the selectivity of gas sensors. Physical methods
include changing morphology and surface structure or the addition of

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 M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

the sieving materials like membranes. Chemical modifications that synthesized LaFeO3 from ethanol to acetone at 200 ◦ C [61]. Another
provide higher selectivity than physical modifications include the study on the gas sensing properties of the Pd-loaded LaFeO3 sensor
addition of sensitizer materials that increase adsorption affinity or spe­ revealed high sensing performance and selectivity toward H2S on 3%Pd
cific reactions between target gas and sensing materials [51]. Each addition at 120 ◦ C [62].
method will be discussed in the following sections.
3.2. Influence of doping elements
3.1. Influence of noble metals decoration
At low operating temperatures, the target gas molecules do not have
Decoration of the sensing materials with catalysts is one of the enough thermal energy to react with adsorbed oxygen species; thus, the
influential methods for the selective detection of the target gases. Cat­ sensor response is too low and it needs some modification for improving
alysts by decreasing the activation energy of the reaction of target gas the sensor’s performance [63]. Some of the sensor’s parameters such as
and sensing materials, increase the reaction rate. Addition of the cata­ stability, sensitivity, selectivity, and response/recovery time are modi­
lysts like noble metals by catalyzing the target gas adsorption, dissoci­ fied by adding dopants during synthesis and with deposition of the
ation, and oxidation enhances the selectivity of the sensors [51]. The sensing layer. The dopants improve sensing properties by enhancing the
addition of catalytically active metals improves the sensitivity and desirable properties or reducing the undesirable properties.
selectivity of sensors. Noble metals enhance sensitivity and lower The LnFeO3 (Ln = La, Sm) perovskite materials have been studied
response/recovery time through surface modification, while transitional extensively and they have exhibited good sensitivity to CO and NO2
metals improve catalytical activity by modifying the morphology of the gases [64–69]. As reported previously, the conductivity of SmFeO3 is as
sensing layer [52]. low as 10− 10 S even at 250 ◦ C, while the conductivity of SmCoO3 is
There are two general ideas for describing the mechanism of metal significantly higher than that of SmFeO3, which can cause low sensi­
sensitizers on the surface of the metal oxides (Fig. 5). Electronic sensi­ tivity of the sensor [70]. As the conductivity of the perovskite material
tization occurs by adjusting the charge carrier concentration [27,34]. can be optimized by B-site substitution because of its ability to create
Many studies have been made on examining the effect of acceptor oxygen vacancy, the effect of cobalt substitution on SmFeO3 has been
doping on semiconductors to lower the concentration of electron charge explored [71]. The sensing properties of SmFe1-xCoxO3 synthesized by
carriers in n-type semiconductors to make them more sensitive to pyrolysis against NO2 and O3 were examined by Itagaki et al., in 2007
reducing gases [53–55]. In electronic sensitization, the redox state of the [36]. They found that with an increase in Co content, the conductivity
sensitizer changes, causing altered resistance in the sensing material. On increased, while the activation energy decreased up to x ≥ 0.2. With
the other hand, in chemical sanitization, the target gas is partially increasing cobalt content, the operating temperature diminished and for
oxidized by a sensitizer, which is then oxidized by adsorbed oxygen a value of greater than 0.2, the conductivity reached a measurable value
species on the surface of the oxide [56]. For instance, Pt nanoparticles even at room temperature. Given the increased conductivity of the
work as an electronic sensitizer and can change oxidation states when SmFe1-xCoxO3 perovskites upon exposure to oxidative gases of NO2 and
the surface is exposed to the target gas. An XPS analysis of the WO3/Pt O3, the p-type feature of the semiconductor was confirmed. The sensor
revealed that the Pt species were oxidized to PtO in an air atmosphere response to the 0.4 ppm O3 rose by lowering the operating temperature
and the Pt+2 were detected, while the XPS analysis of the sample after for x values of 0.05, 0.1, and 0.15, while the maximum response to 10
exposure to CO indicated only reduced species (Pt0) [57]. Meanwhile, ppm NO2 was achieved at 200 ◦ C [36]. It has been reported that partial
the improved sensing mechanism of Au–MoO3 can be explained by the substitution of Sm in SmFeO3 by Ce would improve its conductivity and
chemical sensitization of Au by catalytic dissociation of the oxygen thermal stability [72]. By taking advantage of Ce doping, Sm0.95Ce0.05
molecules on Au surface, which causes plenty of ionized oxygen spill­ Fe1-xCoxO3 have been synthesized [73]. The gas sensing properties of the
over on the MoO3 surface [58]. Hao et al. have shown that the sensing synthesized sample with different levels of Co have been studied where
ability of the hydrothermally synthesized LaFeO3 toward formaldehyde the maximum sensitivity at room temperature was obtained at x = 0.03.
has been increased 4 times by the addition of the Au nanoparticles. The improvement in sensitivity at room temperature could be attributed
Because of the higher work function of the Au (5.1 eV) than LaFeO3, to the increase in oxygen vacancy by Co doping.
some of the electrons of the LaFeO3 conduction band flow to the Au In 2017, Moharamzadeh et al. [74] investigated the Cu-doped in­
nanoparticles to balance the Fermi levels that increase the hole con­ dium tin oxide (ITO) ammonia sensing properties at room temperature.
centration at the surface of the LaFeO3 and the sensitivity of the sensor The FE-SEM study indicated that the dopant did not effect on the
increase [59]. The ethanol sensing ability of the LaFeO3 gas sensor has morphology of the synthesized nanoparticles spin-coated on flexible
been improved by the addition of the Ag and higher response (155 to­ substrates. The results revealed that the sensitivity of the sensor
ward 100 ppm ethanol) with the short response (30s) and recovery times improved upon increasing the amount of dopant up to 4%. The dopant
(5s) achieved at 190 ◦ C than LaFeO3 that can be related to electronic had a significant effect on the response time of the sensor and reduced it
sensitization and chemical sensitization of the Ag on the surface [60]. from 10-12s–7s. Cu doping in ITO, upon increasing the active surface of
The sensing study on the Pd-loaded LaFeO3 sensor showed specificity the ITO, enhanced the Lewis acid-base interaction of NH3 (Lewis base)
against acetone. 2%Pd-loading shifted the selectivity of sol-gel and Cu2+ (Lewis acid) which would directly affect the sensitivity,
response/recovery time, and reproducibility.
The BaTiO3, as an important perovskite material, has been studied
extensively for its tunable dielectric properties [75,76], and the gas
sensing application of the doped perovskite has attracted a great deal of
attention [77–79]. Hydrothermal synthesized Strontium (Sr) doped
barium titanate (Ba0.75Sr0.25TiO3) was studied for ammonia sensing
under humid air and room temperature [45]. The sensor response
exhibited 10% variation relative to the maximum 70% RH. The best
response/recovery time (1 and 15 min) to NH3 was obtained at 30% and
50% RH.
In 2019, Patil et al. [80] examined the sensing properties of syn­
thesized lanthanum (La) doped barium titanate (BaTiO3) via the hy­
drothermal method. The oxygen vacancy could be produced on BaTiO3
Fig. 5. Electronic and chemical sensitization of the noble metals. by substituting trivalent ions including La, Sb, and Y on the barium site.

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M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

Ionic radii are the most effective parameter in deciding substitution sites 3.3. Influence of composite formation
for doping. According to the ionic radii of the La3+(1.15 A◦), it is highly
suitable for Ba2+ (1.35 A◦) site. The XRD results illustrated an increase To ameliorate the performance of the sensing materials composite
in crystallite size upon increasing the La concentration from 0.2% to formation is another influential method. The NiTiO3/TiO2 nano­
0.4% and 1%. The A-site substitution by La caused the formation of the composites with an average crystallite size of 17 nm were synthesized by
Ti vacancies, which affected the dielectric properties of BaTiO3 [81]. the sol-gel method and investigated for sensing LPG at room tempera­
Approximately, 60% yield of doping was determined by ICP-AES anal­ ture. The selectivity of the sensor toward LPG was attributed to the
ysis. The XPS analysis revealed the adsorbed oxygen was more dominant catalytic activity of Ni in dissociating the LPG molecules. The electrical
than the lattice oxygen in samples with 0.2% La, a property that has a conductivity of the metal oxide can be increased by adding the metal
critical impact on the gas sensing mechanism. The sensing response of catalyst. The very fast response/recovery time (about 2s) was related to
samples to NH3 and NO2 at room temperature was greater than that of the whiskers-like structure of the NiTiO3. As long as the energy level of
other gases and it diminished by increasing the temperature to over the TiO2 is located above the conduction band of NiTiO3, the electron
50 ◦ C. The highest response was obtained for the 2% La sample with transition from Ti 3d to Ni 3d would obtain more electrons for the ab­
responses of 78 for NH3 and 165 for NO2, while the undoped sample did sorption of oxygen molecules [90]. The SmFeO3/MoS2 nanocomposites
not respond to them at ambient temperature. The higher polarization of were synthesized by electrospinning combined with the hydrothermal
La-doped BaTiO3 is caused by stronger tetragonal distortion, resulting in method and the humidity-sensing properties of the synthesized mate­
higher adsorption of NH3 and NO2 gases. Another study by the same rials at room temperature were investigated. The composite material
authors in 2020 [39] also examined the Sr doping effect on BaTiO3 gas showed improved sensitivity toward humidity in comparison with MoS2
sensing performance. The Sr-doped BaTiO3 (BaSrTiO3) was synthesized and SmFeO3. The XPS results indicated higher absorbed oxygen that
via a low-temperature hydrothermal method. The TEM and SEM anal­ results in higher function hydroxyl groups on the surface of nano­
ysis revealed enlarged particle size upon increasing the doping con­ composites than SmFeO3 which is beneficial for more water molecules
centration. The highest response to NH3 and NO2 at room temperature absorption [91].
was obtained when the Sr content was 0.2% (88 for NO2 and 57 for Graphene exhibited excellent sensing performance and high surface
NH3). As studied earlier, the pristine (BaTiO3) was selective to H2S and it area which is beneficial in increasing the sensitivity of the sensors in the
did not show any response to NH3 and NO2 at room temperature [82], detection of the target gases. Graphene-based composite materials have
while the selectivity of the BaSrTiO3 to these gases can be caused by been studied for the detection of various gases at low operating tem­
changes in microstructure, ferroelectric, and dielectric properties [83]. peratures. The composites of perovskite oxide and reduced graphene
The photoluminescence spectra emphasized the formation of the donor oxide are promising sensing materials in the detection of the target
level in the band gap, confirming that Sr-doping induced the n-type gases. Sharma et al. have studied the sensing properties of the rGO-
behavior in BaTiO3. Thus, under the positive voltage bias, high polari­ LaFeO3 toward NO2 and CO. High response of the rGO-LaFeO3 com­
zation occurred at Sr-doped samples which would lead to the adsorption posite toward NO2 is attributed to the higher surface area and active
of the NH3 and NO2 at room temperature on the surfaces of the samples. sites of rGO-LaFeO3 [92]. Acetone sensing properties of the hydrother­
Table 1 summarizes the effects of various types of doping on gas sensing mally synthesized ZnSnO3 and 4% rGO-ZnSnO3 have been studied and
properties such as operating temperature, plus response and recovery results indicated that the operating temperature of the sensor 70 ◦ C
times of the BaTiO3 gas sensor. reduced. The electron transport capacity of the composite material is
LaCoO3 (LCO) due to its high p-type electronic conductivity, improved by the high carrier mobility of the rGO and higher sensitivity
considerable mobility of oxygen-ion, and catalytic activity are regarded is achieved at a lower temperature. Formation of the p-n junction be­
as a popular material for gas sensing applications [88]. The doping of the tween ZnSnO3 and rGO induced electron transfer from ZnSnO3 to rGO
p-type LCO nanostructure by Sr2+ would heighten the concentration and and another depletion layer formed which provides higher active sites
induce resistance variations of LCO, as well as enhance the acetone and higher sensitivity [93]. Another study has shown that addition of
sensing performance at room temperature. Room temperature sensing of the rGO until 3% increased the formaldehyde sensing ability of the
the acetone can be attributed to the catalytic activity of the Co3+ at the ZnSnO3 at the low operating temperature of the 103 ◦ C. The fast
surface. The substitution of the La3+ by Sr2+ expands the hole accu­ response speed of the sensor is related to the high surface for adsorption
mulation layer by converting Co3+ to Co4+ which leads to increased and diffusion of the gas and fast carrier transport [94].
resistance variations and sensor sensitivity [42]. Polymer-based composite materials especially conductive polymers,
Recently, the ethanol sensing property of the Ce-doped LCO has been provide highly selective sensing properties. PPy one of the conductive
studied [89]. The results indicated by elevating the Ce concentration, polymers attains lots of attention due to its ease of fabrication, high
the second phase CeO2 was formed and because of the difference in work electrical conductivity, and stability. The gas sensing property of PPy/
function, p-n heterojunction was formed. The Ce doping effectively ZnSnO3 composites to NH3 was studied. Higher sensitivity to NH3 is
reduced the grain size, where favorable ethanol sensing was obtained by related to the fine electron transfer pathway that is provided by PPy
the La0.95Ce0.05CoO3 sample with the shortest response/recovery times polymer [95]. Polyaniline (PANI) is another useful polymer in sensor
(16/8s) at room temperature. applications due to its stability, ease of synthesis, and controllable redox
and electrical properties. The CO2 sensing properties of PANI/LaFeO3
have been studied at room temperature. The higher sensitivity,
long-term stability, and reproducibility were obtained when the LaFeO3

Table 1
Effect of doping on gas sensing properties of the BaTiO3 gas sensor.
Material Target gas Concentration (ppm) Response Response time Recovery time Operating temperature Ref

BaTiO3 CO2 500 10% 2 min 4 min 200 ◦

C [84]
La doped BaTiO3 NH3/NO2 1000 78/165 16–23 s RT [80]
Sr doped BaTiO3 NH3/NO2 1000 57/88 6–19 s RT [39]
Ba0.75Sr0.25TiO3 NH3 1 min 15 min RT [45]
CuO/BaTiO3 CO2 300 s 320 s 160 ◦
C [85]
Ag@CuO/BaTiO3 CO2 700 1.4 <10 s <10 s 120 ◦
C [86]
Cr2O3-doped BaTiO3 NH3 100 ∼ 110 3s 20 s 350 ◦
C [87]

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M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

percentage reached 10% at composite material [96]. The ammonia temperature of 350 ◦ C and thicknesses of 600 nm and 800 nm, respec­
sensing properties of the polymer-based polyaniline/SmBaCuMO5+δ (M tively. The surface roughness influences the gas sensitivity because of
= Fe, Co, Ni) have been studied by Hongxia et al. [97]. They explored the higher surface-to-volume ratio [114]. The XRD pattern indicated the
the gas sensing ability of the sol-gel prepared samples. The results orthorhombic structure of perovskite samples and it demonstrated that
indicated the PANI/SBCM samples had quick responses to 100 ppm NH3 the crystallinity increased upon enlarging the film thickness. The
at room temperature. PANI/SmBaCuFeO5+δ had shorter response/r­ maximum response to the 1 ppm of NO2 gas was obtained at 25 ◦ C and
ecovery time (10s/91s) in comparison to other samples. The respon­ the nanocubes exhibited a higher response than the network structure
se/recovery time increased with the rise in the ionic radius of the M in and showed excellent catalytic activity upon exposure to NO2 gas. The
the samples. quick response at room temperature can be related to the catalytic ac­
tivity of the nanostructured LaFeO3. Furthermore, the higher surface
3.4. Influence of morphology area of the nanocubes (92.85 m2g-1) versus the network structure (76.5
m2g-1) explained the higher signal of the nanocubes. The effect of the
The sensing properties of materials are greatly influenced by surface- morphology on the sensing performance of the LaFeO3 is summarized in
to-volume ratios of the surface morphology. Hence, many studies have Table 2.
dealt with the morphological effects of synthesized materials such as Among all nanostructured semiconductor materials, long one-
bulk materials [98], thick films [99], thin films [100,101], and nano­ dimensional (1D) nanostructured materials with small diameters have
materials [102] on their sensing performance. Nanostructures have gained massive attention because of providing a large specific surface
received considerable attention as sensing materials because of having area [116–118]. One-dimensional nanostructures including nanotubes
large surface area-to-volume ratios [103,104]. As mentioned earlier, [119], nanorods [101,120], and nanowires [121–123], have been
grain size has an important effect on the sensing performance of semi­ considered by many researchers due to possessing a high
conductors. When the grain size diminished to equal to or smaller than surface-to-volume ratio and small grain size. The effects of the
twice the Debye length, the crystallites became fully depleted; thus, the morphology of LaCoO3 nanofibers on their sensing performance and
whole grain would contribute to charge transfer, which leads to operating temperature have been studied [124]. The morphology of the
enhanced sensor response [105]. Note that using ultra-small metal oxide synthesized nanofibers was controlled by altering the annealing tem­
particles, the risk of agglomeration increases. In that case, the specific perature. Upon elevation of the temperature from 550 ◦ C to 700 ◦ C, the
surface area and diffusion of the gas in the sensing layer would diminish crystalline structure transformed into a more stable rhombohedral from
[106,107]. Researchers have demonstrated that by controlling the syn­ the cubic structure. Synthesis of the nanofibers reduced the operating
thesis parameters, different morphologies with high porosity and spe­ temperature of the sensors to 120 ◦ C whereas the sensors with an
cific surface area can be achieved, which can reduce the operating annealing temperature of 650 ◦ C had the best selectivity as well as fast
temperature. response and recovery times, (26s/66s) which was because of the
Recently, many studies have focused on achieving uniform materials highest porosity. The obtained results were interesting though some
with controllable morphologies. Zhang et al. employed polyvinyl pyr­ effort is still required to reduce the operating temperature to room
rolidone (PVP) to induce and regulate crystal growth using the co- temperature. Recently, sol-gel assisted hydrothermal method synthe­
precipitation method for the synthesis of LnFeO3 (Ln = La, Nd, Sm) sized BaSnO3 nanorods have exhibited a high response of 45.85 toward
materials. Among them, LaFeO3 reached a low detection limit of 1 ppm acetone on the exhaled human breath at the low operating temperature
n-propanol at a relatively low operating temperature of 120 ◦ C [108]. of 80 ◦ C [125].
Nanocrystals of the neodymium iron oxide (NdFeO3) were synthe­ The Pd functionalized mesoporous LaCoO3 nanowires were synthe­
sized via the sonication-assisted precipitation method by Singh et al. sized via the electrospinning method with the CO sensing properties of
[109]. The liquefied petroleum gas (LPG) sensing properties of the the nanowires investigated at low operating temperature of 60 ◦ C [126].
NdFeO3 in the form of solid-state pellets as well as thin films were The SEM and TEM images revealed the porous nanowires had 200–800
investigated. The SEM images exhibited uniform distribution of the nm diameters, nanocrystalline size of 30–60 nm with a pore size of
porous nanobeads with enhanced sensitivity achieved through this type 30–100 nm, and excellent CO sensing properties. The reduced operating
of surface morphology. The maximum sensor response percentage of the temperature of the Pd functionalized LaCoO3 nanowires was related to
thin film sensor and pellet sensor was 8225 and 324. Thus, the nano­ the mesoporous structure and catalytic activity of Pd.
structured porous film was superior in comparison to the pellet sensor
due to well-defined porosity, controllable pore sizes, and homogeneous 4. Future trends and challenges
film thickness. These results were also confirmed by a comparative study
of the SO2 sensing of Ca-doped LaFeO3 pellet vs. thin film [110]. Higher Currently, the high operating temperature of semiconductor gas
sensitivity, as well as lower detection limit and operating temperature, sensors is one of the important challenges that researchers confront.
were obtained by the thin film. The increase in sensor response was Although significant progress at room temperature operation of the
related to the good connection of the nanoparticles which would facil­ perovskite gas sensors has been made, novel strategies and methods
itate the charge carrier movements. should be used. Reducing the operating temperature to room tempera­
Radio frequency magnetron sputtering synthesized LaFeO3 thin films ture is important in terms of stability, power consumption, and safety
on a silicon substrate have been studied by Thirumalairajan et al. [111]. issues.
Given the influence of morphology on performance of sensors, various To overcome the challenges, future research should be focused on
operating parameters have been optimized. However, controlling the not only noble metals and transition metals doping and fabrication of
morphology of perovskite materials is not very simple [112,113]. composites, but also the most recommended solution is optimizing the
Various samples with different film thicknesses and substrate tempera­ properties and micro/nanostructure of sensing materials. For morpho­
tures have been prepared with the sensing properties examined. The logical modifications, unique three-dimensionally ordered macroporous
SEM images of the samples illustrated that the morphology of the and hierarchical architectures with higher sensing potential can be
samples is associated with the deposition temperature and film thick­ synthesized which can provide more adsorption sites. According to our
ness. Elevation of the deposition temperature has been linked to review, it is found that most of the previous studies focused on mono-
increased mobility of the surface adsorbed atoms, whereby they have metal doping while multi-metals doping can be considered a better
diffused into energetically favorable sites. The SEM and TEM images of idea. The effect of humidity on gas sensing properties of the perovskite
the samples indicate that network and nanocube structures with an gas sensors at room temperature is a troublesome challenge that should
average size of 90 and 70 nm can be achieved at a deposition be considered to solve the related problems.

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M. Souri and H. Salar Amoli Materials Science in Semiconductor Processing 156 (2023) 107271

Table 2
Gas sensing performance of the different morphological LaFeO3 based sensors.
Material morphology particle Target response Target gas concentration Operating temp. Response time Recovery time Ref.
size gas (ppm) (◦ C) (s) (s)

La0.6Ca0.4FeO3 Pellet 52 (nm) SO2 3.6 5 160 35 30 [110]

La0.6Ca0.4FeO3 Thin film SO2 7.6 3 120 15 14 [110]
LaFeO3 Nanocube thin film 70 (nm) NO2 29.6 1 25 24–11 35–15 [111]
LaFeO3 Network thin film 90 (nm) NO2 10.04 1 25 30–17 42–18 [111]
Ag–LaFeO3 Spherical petal-like 1–2.1 methanol 16.98 5 215 45 50 [115]
Cage (μm)
Ag–LaFeO3 Spherical Core-shell 6.75 (μm) methanol 33.7 5 195 42 57 [115]

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