e-ISSN 2150-5551

CN 31-2103/TB

REVIEW [Link]

Recent Progress on Flexible Room‑Temperature Gas

Sensors Based on Metal Oxide Semiconductor
Cite as
Nano-Micro Lett.
(2022) 14:206 Lang‑Xi Ou1, Meng‑Yang Liu1, Li‑Yuan Zhu1, David Wei Zhang1, Hong‑Liang Lu1,2 *
Received: 12 July 2022
Accepted: 12 September 2022
Published online: 21 October 2022
© The Author(s) 2022

HIGHLIGHTS

• Latest progress on flexible room temperature (FRT) gas sensor based on metal oxide semiconductors (MOS) is comprehensively
reviewed.

• FRT gas sensor based on pristine MOS and MOS modified with noble metal nanoparticles, organic polymers, carbon based materials
and transition metal dichalcogenide materials are meticulously reviewed.

• The gas sensing mechanism of MOS chemiresistive gas sensors are introduced and the applications, future perspectives, and chal‑
lenges of FRT gas sensors are also proposed.

ABSTRACT With the rapid development of the Internet of Things, there is a great p
al nano articles m
met od
demand for portable gas sensors. Metal oxide semiconductors (MOS) are one of the No
ble ific
at
io
n
most traditional and well-studied gas sensing materials and have been widely used tio
n
a
fic

to prepare various commercial gas sensors. However, it is limited by high operat‑

di
mo

ing temperature. The current research works are directed towards fabricating high-

TM
ers

t
room empe

DCs
olym

le r
performance flexible room-temperature (FRT) gas sensors, which are effective in
xib

at

modification
Organic p

ure
Fle

Gas sensors
simplifying the structure of MOS-based sensors, reducing power consumption, and
expanding the application of portable devices. This article presents the recent research
s
Me

to r
ta

ox
progress of MOS-based FRT gas sensors in terms of sensing mechanism, performance,
uc
l

id e nd
s e mic o
Ca

flexibility characteristics, and applications. This review comprehensively summarizes

rbo
n-

and discusses five types of MOS-based FRT gas sensors, including pristine MOS,
ba

d
se

m ti o
n

at va
noble metal nanoparticles modified MOS, organic polymers modified MOS, carbon- e ri
als
mo ht
a c ti
dific
ation Lig
based materials (carbon nanotubes and graphene derivatives) modified MOS, and
two-dimensional transition metal dichalcogenides materials modified MOS. The effect
of light-illuminated to improve gas sensing performance is further discussed. Furthermore, the applications and future perspectives of
FRT gas sensors are also discussed.

KEYWORDS Metal oxide semiconductor; Flexible gas sensor; Room temperature; Nanomaterials

* Hong‑Liang Lu, honglianglu@[Link]

1
State Key Laboratory of ASIC and System, Shanghai Institute of Intelligent Electronics &Systems, School of Microelectronics, Fudan University,
Shanghai 200433, People’s Republic of China
2
Yiwu Research Institute of Fudan University, Chengbei Road, Yiwu City 322000, Zhejiang, People’s Republic of China

Vol.:(0123456789)
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206 Page 2 of 42 Nano-Micro Lett. (2022) 14:206

1 Introduction It is noticeable that the presence of some specific VOCs is

related to specific diseases [39–41]. Through a simple breath
In the past decade, the Internet of Things (IoTs), the net‑ analysis, many diseases can be diagnosed and therapeutic
works that connects diverse sensors and actuators, has monitored noninvasively [42, 43]. For instance, ammonia
attracted enormous attention [1–5]. Traditional electronic and fatty acids are found in the breath of patients with cir‑
sensors are gradually transforming from bulky solid-state rhosis, while acetone and isoprene are found in the breath of
devices to portable, high-performance, and multifunctional patients with diabetes [44–46]. However, the conventional
devices. The rapid development of flexible electronics makes technology of breath analysis requires bulky and expensive
them play a significant role in the wide applications of IoTs, equipment, long time-consumption and well-trained per‑
which serves as an ideal platform for wearable devices sonnel. Therefore, there is an increasing requirement for
[6–12]. In recent years, flexible and wearable devices have high-performance gas sensors with low-cost, high sensitiv‑
been used as attractive alternatives to bulky analytical instru‑ ity, rapid response, fabulous selectivity, and low limit of
ments and applied to perform continuous physiological detection (LOD).
monitoring of body movement, blood temperature, blood Mechanically flexible gas sensors are one of the most pop‑
glucose, heart rate, and electrophysiological activities such ular and forefront research directions of IoTs, meeting the
as electroencephalography, electrocardiography, and elec‑ enormous industrial requirements of smart wearable devices
tromyography [13–16]. Recently, metaverse has become a [47]. Moreover, they are crucial for monitoring environmen‑
hot issue. Metaverses are sensory-rich virtual worlds where tal gases, gaseous pollutants, volatile hazards, humidity,
people engage with each other as virtuous avatars without exhaled gases, body odor, nerve agents or explosives, and
any physical limitations [17, 18]. Wearable devices integrat‑ food quality. Conventional gas sensors are typically manu‑
ing kinds of sensors, which can conduct continuous physi‑ factured on inorganic substrates, including quartz, glass,
ological monitoring and real-time interaction with software alumina ceramic tubes and silicon wafers. However, their
agents, are of vital importance to the rapid development of rigidity and fragility limit their application in a variety of
metaverse [19]. new fields. In contrast, the integration of gas sensors on flex‑
Various hazardous gases are released from industrial and ible substrates, such as polymer, textiles, and paper-based
agricultural processes, such as CO, ­NOx, ­NH3, ­H2, ­H2S, and substrates has attracted the increasing attention of research‑
volatile organic compounds (VOCs), including ethanol, ers over the past few years, making them highly promising
isopropanol, acetaldehyde, and formaldehyde [20–23]. The in the fields of portable electronics [48–51], smart textiles
leakage of these pollutant gases will not only pollute the [52–54], radio frequency identification (RFID) [55–59], and
environment, but also have a detrimental effect on human medical health [60–62]. However, the sensing performance
body [24–27]. For instance, emissions of ­NOx from coal of flexible gas sensors including response value, selectivity,
fired power stations lead to ozone holes, acid rain and severe response/recovery time, and LOD is largely influenced by
haze in metropolitan areas, causing serious damage to human operating temperature, which generally require the configu‑
health, the ecological environment and the national economy ration of microheaters, resulting in high energy consump‑
[28–30]. In particular, serious air pollution can damage the tion, great complexity of microstructure, and limitations
lungs of humans, facilitating the transmission and infection of applications [63]. Therefore, the flexible gas sensors
of COVID-19 [31–34]. Real-time detection of toxic gases operating at room temperature (RT) are gradually arousing
in industrial production and the development of wearable extensive attention. Their portability, excellent mechanical
gas warning devices are of significant to workers, especially flexibility in harsh environments, and low energy consump‑
in environments where toxic gas leaks can occur. In addi‑ tion make them promising for various applications. Recently,
tion to the need for timely detection of hazardous gases, flexible room-temperature (FRT) MOS-based sensors have
the detection of specific gases is also widely used in the ­ O2 [54,
been reported to detect a variety of gases, including N
area of medical healthcare [35]. Gas chromatography–mass 64–78], ­NH3 [79–89], ­H2 [90–94], ­H2S [68, 95–98], ­C2H2
spectrometry analysis of human exhaled gas showed that the [99], ethanol [100–103], acetaldehyde [104], formaldehyde
exhaled gas contains more than 870 different VOCs [36–38]. [105], acetone [106], ozone [107], isopropanol [108], tri‑
methylamine [109], and triethylamine [110, 111]. Beyond

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 3 of 42 206

that, some reported FRT gas sensors have been applied

tal nanoparticles m
to practical applications, such as smart face masks [100], me od
ble ific
No ati
on
E-textiles [54, 104], passive wireless RFID [112], disease n
tio
detection [98], and large-scale flexible sensors array [65,

a
fic
di
113], exhibiting broader application prospects in the fields of

mo
IoTs, metaverses, industrial production, medical application,

TM
ers
t
room empe

DCs
lym
etc. Nowadays, personalized wearable FRT gas sensors are le r

xib

at

mod
Organic p

ure
extensively employed to monitor the exhaled gas of patients

Fle
Gas sensors

ification
while they are out of hospital and provide sufficient infor‑

Me

s
mation [48, 114]. For example, ketogenic diets (KDs) can

to r
ta
ox
perform more effective weight loss when cooperated with

uc
l
id e nd
s e mic o

Ca
a FRT acetone gas sensor monitoring the concentration of

rb o
exhaled acetone [115, 116].

n-
ba
d
The FRT gas sensors have high requirements for sensing

se
m io

n
at at
e ri tiv
materials that not only perform well at RT, but also under als
mo ht
ac
dific Lig
bending conditions. In general, traditional gas sensing mate‑ ation

rials including metal oxide semiconductor (MOS), con‑

ducting polymers, and carbon-based materials [117–122].
Fig. 1  The strategies to achieve high-performance FRT MOS-based
Among them, MOS is the most popular commercial sensing chemiresistive gas sensors
material due to its merits of easy synthesis, high response
value, low cost, short response/recovery time, great revers‑
such as morphological modification of pristine MOS, noble
ibility, and excellent stability [123–129]. However, its disad‑
metal nanoparticles modified MOS, light-illuminated MOS,
vantages such as high-temperature operation and high-power
and two-dimensional (2D) transition metal dichalcogenides
consumption hinder its wearable applications [130–132].
(TMDCs) modified MOS. Table 1 summarizes various
What’s worse, high-temperature operation not only degrades
reported MOS-based FRT sensors.
the nanostructure of the sensing material, deteriorating the
Several reviews based on flexible gas sensors have also
gas sensing performance, but also hinders the detection of
been published, introducing carbon-based [49, 143, 144],
explosive or flammable gases. Therefore, the ability of the
organic polymers-based [145], and TMDC-based [146] gas
MOS-based sensors to work at RT is of vital significance
sensors. In addition, several reviews dedicated to RT gas
because it leads to very low power consumption and simpli‑
sensors have been published, discussing the development
fies the sensor structure. At the meantime, the conducting
of various nanostructured materials-based RT gas sen‑
polymers-based sensors can operate at RT without addi‑
sors [120, 132, 147, 148] and MOS-based chemiresistive
tional power requirements, but their performance degrades
RT gas sensors [118, 149]. However, no comprehensive
in humid environment. In addition, the carbon-based mate‑
review focusing on the recent advances on MOS-based
rials can also greatly lower the operating temperature and
FRT gas sensors is available. Consequently, this review
contribute to high sensitivity, but long response/recovery
will systematically summarize and analyze the sensing
time and complex processes render them inadequate for wide
mechanisms and recent advances in FRT MOS-based gas
application [98, 133–135]. To achieve high-performance
sensors based on pristine MOS, noble metal nanopar‑
FRT MOS-based chemiresistive gas sensors, optimization
ticles modified MOS, organic polymers modified MOS,
has been performed from material design and alternate
carbon-based materials modified MOS, TMDCs materials
activation, which is graphically presented in Fig. 1. The
modified MOS. In addition, the effect of light-illuminated
thought of combining MOS with conducting polymers or
on improving the gas sensing performance is further dis‑
carbon-based materials is proposed owing to the integrated
cussed. The current applications of FRT gas sensors are
advantages of both components [136–142]. Beyond that,
also summarized.
a number of strategies have been used to improve sensing
performance of MOS-based FRT gas sensors up to now,

13
 Table 1  Sensing performance of various MOS-based FRT gas sensors 206
Material Structure Substrate Synthesis Target gas C (ppm) Response τres/τrec LOD Bending cycles Response References
method decrease/bend‑

© The authors
ing cycles

Part A: Sensing performance of pristine MOS FRT gas sensors

Page 4 of 42

ZnO Nanowires PET Hydrothermal H2 1,000 5c ~ 600/s – – – [90]

ZnO Nanorods Nylon Hydrothermal H2 500 109c 149/122 s – – – [92]
ZnO Nanoparticles PET – Ethanol 800 2.2a – – – – [102]
ZnO1-x Sheet-like PP Suspension NO2 1 2.568b 60/230 min 0.25 ppm – – [70]
flame spraying
ZnO Nanoparticles Cotton fabrics Sol–gel Acetaldehyde 100 33c 228/14 s – – – [104]
In2O3 Cubic crystals PVA Hydrothermal Ethanol 100 ~ 1.4a 5/3 s 10 ppm – – [103]
In2O3 Octahedral PI Oxidation NO2 5 5.75a 105/785 s 3 ppm – – [69]
nanopowders
In2O3 Nanowires PI Electrospun NO2 0.5 5.52 – 10 ppb – – [78]
InOx Thin films PET Magnetron sput‑ Ozone 1.07 ~ 72.5c 7/min 15 ppb – – [107]
tering
TiO2 Thin films PET Spinning Formaldehyde 5 > ­570b 9/ ~ 300 s 3.8 ppb 200 No obvious [105]
decrease
TiO2 Nanotubes PI Anodization TMA 400 150c ~ 25/s 40 ppm – – [109]
CuO Nanorectangles PET Hydrothermal NH3 5 ~ 0.25b 90/120 s 5 ppm – – [82]
Cellulose/Fe2O3 Nanoparticles PET Hydrothermal NO2 200 ~ 1,100c 50/30 s 2 ppm – – [71]
WO3-δ Films PI Granule spray NO2 10 18,500c 17/25 s 1.88 ppm 4,000 < 66.7%/4,000 [76]
SnO2/ZnO Nanofibers PET/PDMS/ Electrospun NO2 0.1 56c – 0.1 ppm – – [233]
Paper
Part B: Sensing performance of noble metal nanoparticles modified MOS FRT gas sensors
Ga/ZnO Nanorods PI Hydrothermal H2 1,000 91c ~ 18.8/s 0.2 ppm – – [91]
Pd/ZnO Nanorods PI/PET Hydrothermal H2 1,000 91.2c ~ 18.8/s 0.2 ppm 106 13%/105, [93]
52%/106
Ag/ZnO Nanorods PI Hydrothermal C2H2 1,000 26.2a 66/68 s 3 ppm 104 10.6%/104 [99]
Pt/SrGe4O9 Nanotubes PET Electrospun NH3 100 7.08a 17/16 s 1 ppm 1,000 No obvious [80]
decrease
PANI/Rh/SnO2 Nanotubes PET Electrospun NH3 100 13.6 113/159 s 500 ppb 1,000 21% [172]
PANI/In2O3/Au Nanospheres/ PI Hydrothermal NH3 100 46a 118/144 s – 100 No obvious [79]
Nanofibers decrease
SWCNT/PdO/ Nanocubes PI Chemical pre‑ NO2 20 27.33c – 1 ppm 4,000 No obvious [74]
Co3O4 cipitation decrease
Part C: Sensing performance of organic polymers modified MOS FRT gas sensors

[Link]
Nano-Micro Lett. (2022) 14:206
 Table 1  (continued)
Material Structure Substrate Synthesis Target gas C (ppm) Response τres/τrec LOD Bending cycles Response References
method decrease/bend‑
ing cycles

PANI/WO3 Nanofibers/ PET In situ polymeri‑ NH3 10 7a 13/49 s 500 ppb – – [87]
Flowerlike zation
PANI/CeO2 Nanosheet/ PI Self-assembly NH3 50 262.7c 14/6 min 16 ppb 500 No obvious [83]
Nanoparticle decrease
PANI/α-Fe2O3 Nanofiber/Nano‑ PET Sol–gel NH3 100 72c 50/1575 s 2.5 ppm – – [81]
particle
Nano-Micro Lett. (2022) 14:206

PANI/Fe2O3 Sea cucumber- PET Hydrothermal NH3 100 6.12a 100/s 0.5 ppm – – [85]
shaped
PANI/α-Fe2O3 Nanofiber/Nano‑ PET In situ polymeri‑ NH3 100 39c 27/46 s 5 ppm – – [89]
particle zation
PANI/CoFe2O4 Nanofiber/Nano‑ PET In situ polymeri‑ NH3 50 118.3c 24.3/ ~ 410 s 25 ppb 500 3.4%/500 [84]
particle zation
SnO2@PANI Nanoparticles/ PET Hydrothermal NH3 100 29.8 125/167 s 10 ppb 100 No obvious [234]
Nanofiber decrease
PANI@SnO2 Nanoparticle/ PET In situ polymeri‑ NH3 100 29a 34/s > 1.8 ppm – – [86]
Nanofibers zation
PANI/SnO2 Nanofibrous/ PET In situ polymeri‑ TEA 100 69a ~ 5/s 1.2 ppm – – [110]
Nanoparticle zation
PANI/MoO3 Nanorods/Nano‑ PET In situ polymeri‑ TEA 100 22.6a 35/88.42 s 0.55 ppm – – [111]
particle zation
PANI@SnO2/ Nanofiber/Nano‑ PET In situ polymeri‑ NH3 100 20.4 46/54 s 500 ppb 500 26.5%/500 [186]
Zn2SnO4 sphere zation
ZnO/S, N: Nanopolyhedra/ PET In situ polymeri‑ Acetone 0.5 2c 15/27 s 0.1 ppm 60 No obvious [106]
GQDs/PANI Nanorob zation decrease
Chitosan/WO3/ Nanocomposite Chitosan/IL Sol–gel H 2S 200 2.75a ~ 13.6/s 15 ppm – – [97]
IL membranes
CMC/CuO/IL Nanocomposite CMC/IL Hydrothermal H 2S 300 ~ ­20c ~ 52 15 ppm – – [95]
membranes
PVA/WO3/IL Nanocomposite PVA/IL Sol–gel H 2S 300 ~ ­12c ~ 19.1/s 10 ppm 5 No obvious [96]
membranes decrease
Part D: Sensing performance of carbon-based materials modified MOS FRT gas sensors
MWCNT/WO3 Nanoparticles PET Hydrothermal NO2 5 14c 10/27 min 0.1 ppm 108 0.7%/106, [73]
2.1%/108
MWCNT/WO3/ Nanoparticles PI/PET Hydrothermal NO2 5 17c 7/15 min 1 ppm 106 No obvious [72]
RGO decrease

13
Page 5 of 42 206
 Table 1  (continued)
206
Material Structure Substrate Synthesis Target gas C (ppm) Response τres/τrec LOD Bending cycles Response References
method decrease/bend‑

© The authors
ing cycles

MWCNT/Co3O4 Nanofiber Textile fabric Heat treatment NO2 1,000 ~ ­32c – 0.1 ppm – – [64]
Page 6 of 42

SWCNT/Fe2O3 Nanospheres PP CVD NO2/H2S 10/100 19/18.3c 300/300 s 1 ppm 16 No obvious [68]
decrease
SWCNT/CuO Flower-shaped PP Hydrothermal H2S 1 ~ ­35c 7/28 s 100 ppb – – [112]
SWCNT@ZnO Quantum dot Nylon Redox reaction Ethanol 500 1.09a 992/301 s – 1,000 No obvious [100]
decrease
RGO/ Nanoneedles PET Hydrothermal Isopropanol 100 4.96a 60/s 1 ppm 100 No obvious [108]
WO3·0.33H2O decrease
In2O3@RGO Nanoparticles PI – NO2 1 31.6c 4.2/13.3 min 50 ppb – – [65]
RGO/ZnO Nanosheet Cotton/elastic – NO2 15 44c 140/630 s 0.2 ppm 3,000 No obvious [54]
threads decrease
Graphene/CdO Nanoparticles – – LPG 600 77c – 100 ppm – – [213]
RGO/SnO2 Nanoparticles PI Spraying NO2 100 0.2640b 412/587 s 20 ppm 1,000 10.3%/1,000 [231]
RGO/SnO2/ Hot-press thick PVDF Hot press H2 100 49.2c 34/142 s 0.5 ppm – – [94]
PVDF film
SnO2/RGO/ Hollow spheres PET In situ polymeri‑ H2S 2 60.11c 82/78 s 50 ppb 60 No obvious [98]
PANI zation decrease
Part E: Sensing performance of TMDCs materials modified MOS FRT gas sensors
SnO2/SnS2 Nanotubes PET Hydrothermal NH3 100 2.48a 21/110 s 1 ppm 3,000 No obvious [88]
decrease
SnO2/MoS2 Thin films PET E-beam evapo‑ NO2 9 7.57 – 3 ppm – – [222]
ration
Au/SnO2/WS2 Nanotubes PI Sol–gel NH3 50 3.687 ~ 180/ ~ 330 s 0.5 ppm 10,000 20.26%/1,0000 [221]
Part F: Sensing performance of inorganic materials modified MOS FRT gas sensors
In2O3/g-C3N4 Nanofibers Yttria-stabilized ALD NO2 1 7.2a 31/44 s 50 ppb – – [66]
zirconia
Part G: Sensing performance of IGZO based thin-film transistors FRT gas sensors
IGZO Thin films PI CVD NO2 5 ~ 1.3a – 2 ppm – – [75]
IGZO Nanofiber net‑ PEDOT:PSS Blow-spinning NO2 20 33.2c 5/5 s 20 ppb 1,000 No obvious [67]
work decrease

C: concentration; τres/τrec: response time/recovery time; R ­ esponsec:

­ esponsea = Ra/Rg (reducing gas) or Rg/Ra (oxidizing gas); ­Responseb: ΔR/Rg (reducing gas) or ΔR/Ra (oxidizing gas); R
ΔR/Rg × 100% (reducing gas) or ΔR/Ra × 100% (oxidizing gas). Ra: resistance of the sensors exposed to the background gas, Rg: resistance of the sensors exposed to the target gas, ΔR: the
change in resistance of the sensors after exposure to the target gas
PET Poly(ethylene terephthalate); PP Polypropylene; PVA Polyvinyl alcohol; PI Polyimide; PDMS Poly(dimethyl siloxane); PVDF Polyvinylidene fluoride; PEDOT:PSS Poly(3,4-ethyl‑
enedioxythiophene) polystyrene sulfonate; IL Ionic liquid; CMC Carboxymethyl cellulose; TMA Trimethylamine; TEA Triethylamine; LPG Liquid petroleum gas; PANI Polyaniline; GQD
Graphene quantum dots; SWCNT Single-walled carbon nanotubes; MWCNT Multi-walled carbon nanotubes; Mxene Transition metal carbides and carbonitrides; RGO Reduced graphene
oxide; IGZO Indium gallium zinc oxide

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Nano-Micro Lett. (2022) 14:206 Page 7 of 42 206

2 Gas Sensing Mechanism of MOS As a result of these processes, the resistance of the sens‑
Chemiresistive Gas Sensors ing layer will change significantly, which will result in the
response of the gas sensor. Therefore, the sensitivity of
2.1 Pristine MOS Gas Sensing Mechanism the MOS-based gas sensors is generally defined as Ra/Rg
(reducing gas), R g/R a (oxidizing gas), ΔR/R g (reducing
The gas sensing mechanism of MOS is based on the oxy‑ gas), ΔR/Ra (oxidizing gas), ΔR/Rg × 100% (reducing gas),
gen adsorption model, which assumes that the change in or ΔR/Ra × 100% (oxidizing gas) (where Ra is the resist‑
resistance is related to chemisorbed oxygen [150–152]. ance of the sensors exposed to the background gas, Rg is
In air, oxygen molecules adsorb on the MOS surface and the resistance of the sensors exposed to the target gas, ΔR
form negatively charged chemisorbed oxygen ( O−2 , ­O −, is the change in resistance of the sensors after exposure
­O2−) by trapping conduction band electrons. The type of to the target gas).
chemisorbed oxygen is related to the operating temper‑ Conventionally, MOS-based gas sensors are operated
ature and species of MOS material, which significantly at 300–500 ℃ to provide sufficient activation energy to
determines the sensing performance of the sensing mate‑ facilitate oxygen adsorption, which is also called thermal
rial [153, 154]. However, the temperature interval corre‑ activation. In contrast, at RT, the chemisorbed oxygen ions
sponding to the presence of chemisorbed oxygen ions on on the MOS surface are mainly O−2 , with a low content of
metal oxides is not well known and varies from different other chemisorbed oxygen ions, making it a challenge to
metal oxides. In general, O−2 is usually chemisorbed when achieve RT operation of MOS. From the perspective of
the temperature is below 100 °C. Once the temperature is material design, in order to achieve RT operation, pris‑
between 100 and 300 °C, O ­ − is generally chemisorbed and tine MOS materials can be nanoconstructed with differ‑
O−2 disappears rapidly. And when the temperature exceeds ent morphologies, facilitating efficient modulation of the
300 °C, the chemisorbed oxygen is mainly in the form of electron depletion layer. In addition, the construction of
­O2− [155]. The process of oxygen ion formation can be heterogeneous structures by surface modification of MOS
summarized by the following equations [156]: materials is also an efficient strategy.

In air ∶ O2 (gas) → O2 (ads) (1)

2.2 Heterostructured MOS‑Based Nanocomposites Gas

T < 100 ◦ C ∶ O2 (ads) + e− → O−2 (ads) (2)
Sensing Mechanism

100 ◦ C < T < 300 ◦ C ∶ O−2 (ads) + e− → 2O− (ads) (3) Generally, MOS are often hybrids with other MOS, organic
polymers, carbon-based materials and TDMCs to signifi‑
T > 300 ◦ C ∶ O− (ads) + e− → O2− (ads) (4) cantly improve their sensing performance. Due to the dif‑
ferent energy band structures of MOS and hybrid materials,
As a result of oxygen adsorption, an electron depletion
electrons or holes are transferred at the interface between the
layer with a low electron concentration is formed on the
components until their Fermi levels equilibrate to the same
surface of the n-type MOS, which has a higher resistance
energy level. This process results in the formation of hetero‑
than the core region due to the reduced number of elec‑
junctions at the interface between the MOS and the hybrid
trons. While on the surface of the p-type MOS, a hole
materials. The formation of the heterojunctions modulates
accumulation layer is formed, which has a lower resist‑
the thickness of the depletion/accumulation layer and the
ance than the core region of the MOS due to the increased
height of the potential barrier, changing the internal electron
number of holes.
distribution between different components and significantly
When exposed to the target reducing gases, the target
affecting the sensing performance of the sensing materials.
molecules adsorb to the surface of MOS sensing layer and
When analyzing the mechanism of MOS nanocomposites,
react with the chemisorbed oxygen ions, releasing elec‑
the effect of heterojunctions needs to be considered primar‑
trons into the MOS material. Conversely, for oxidizing
ily. In this section, the mechanism of heterostructured MOS-
gases, more electrons are trapped from the MOS surface.
based nanocomposites is illustrated with two subsections:

13
206 Page 8 of 42 Nano-Micro Lett. (2022) 14:206

anisotype heterojunction (p–n) and isotype heterojunctions target gases, which improves the sensing performance at
(n–n, p–p). RT. The addition of carbon-based materials to the MOS can
For the anisotype heterojunction (p–n), the Fermi energy also remarkably improve the conductivity of the MOS-based
level of the n-type semiconductor is generally higher than nanocomposite and optimize its sensing properties at RT.
the Fermi energy level of the p-type semiconductor. There‑ The modification of 2D TMDCs can effectively modulate the
fore, when two dissimilar materials with different Fermi heterojunction between MOS and TMDCs due to its unique
levels contact, the electrons are transferred from the n-type surface effect, exhibiting great potential at RT as well. From
semiconductors to the p-type semiconductors, and the holes the perspective of alternate activation, materials with self-
are transferred from the p-type semiconductors to the n-type heating capability can achieve thermal activation without
semiconductors until the Fermi energy levels are balanced. microheaters. Photoactivation also facilitates the reaction
After that, a depletion layer is formed at their interface and with the target gas by introducing additional photogenerated
the energy bands on both sides are bent to create a potential electron–hole pairs, thus enhancing the gas sensing perfor‑
barrier, which makes the electron transport channel nar‑ mance at RT. These specific sensing mechanisms will be
rower. In addition, owing to the wider depletion layer width discussed further in different chapters.
of the heterojunction, the initial resistance increases greatly
compared to the pristine MOS. Therefore, when exposed
3 Pristine MOS FRT Gas Sensors
to an oxidizing gas atmosphere, the increase in resistance
is small. However, when exposed to a reducing gas atmos‑
Pristine MOS generally have great stability, reversibility,
phere, the resistance decreases sharply, which can improve
and their manufacturing process is facile and cost-effective
the selectivity of the sensor to some extent.
[157–159]. Various morphologies of nanostructures for pris‑
For the isotype heterojunction (n–n, p–p), the band bend‑
tine MOS including nanoparticles [71, 97, 101, 102, 104],
ing phenomenon also occurs due to the difference in Fermi
nanorods [92], nanowires [90], nanotubes [109], nanocu‑
energy levels. For n–n heterojunctions, electrons are trans‑
bic crystals [103], nanorectangles [82], sheet-like [70], and
ferred from the side with high Fermi energy levels to the side
columnar [160] nanostructures have been fabricated and
with low Fermi energy levels, while an electron depletion
employed in flexible gas sensors to help reducing operat‑
layer is formed on the side with high Fermi energy levels
ing temperature to RT (Fig. 2). These sensors can be used
and an electron accumulation layer is formed on the other
to detect a variety of gases, including ­NH3, ­NO2, ­H2, ­H2S,
side. Similarly, for p–p heterojunction, holes are transferred
ethanol, isopropanol, trimethylamine (TMA), formaldehyde,
from the side with low Fermi energy levels to the side with
acetaldehyde and ozone, performing with good sensing
high Fermi energy levels, while the hole accumulation layer
performance.
is formed on the side with high Fermi energy levels and the
N-type pristine MOS including ZnO, ­In2O3, ­WO3, ­Fe2O3,
hole depletion layer is formed on the other side.
and ­TiO2 are the sensing materials that have been reported
Generally, to achieve RT operation and enhanced sensing
for FRT chemiresistive gas sensors. Among these materi‑
performance of MOS-based gas sensors, two perspectives
als, ZnO has been a fascinating FRT gas sensing material
can be considered: material design and alternate activation.
attributed to the fusion of its inherent characteristics such
From the perspective of material design, for pristine MOS,
as high electron mobility, wide bandgap, excellent chemi‑
reducing the grain size, constructing various morphologies
cal stability, non-toxicity and biocompatibility as well as
with enhanced surface-to-volume ratio are considerable
its versatility in fabricating various nanostructures such as
sensitization strategies. In addition, chemical and electronic
nanorods [92], nanowires [90], nanoparticles [102, 104],
sensitization can be achieved by decorating precious metals,
columnar [160], and sheet-like [70] nanostructures. Moham‑
which can significantly improve the sensing performance
mad et al. [92] fabricated hexagonal-shaped and well-
under RT. Hybridizing with some unique materials that can
aligned ZnO nanorods assembled on nylon substrates using
chemically react with the target gas is also an effective way
hydrothermal method. The high specific surface area and
to achieve RT operation. For instance, PANI reduces from
high crystalline quality of ZnO nanorods contributed to the
the conductive emeraldine salt state to the non-conductive
good response of 109% to 500 ppm hydrogen ambient with
intrinsic emeraldine base state when reacting with certain

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Nano-Micro Lett. (2022) 14:206 Page 9 of 42 206

promising application in wearable gas sensing devices with

UV filtering capability.
In2O3 is also an outstanding material for FRT gas sensors
due to its excellent low-temperature gas sensing properties
WO3
and the ability to synthesize different controllable morphol‑
Fe2O3
7%
7%
ogies. ­In2O3 cubic crystals were prepared by a modified
hydrothermal synthesis [103] and then made into a flexible
CuO Pristine
ZnO
composite film by blending with polyvinyl alcohol (PVA).
p-type

13% metal oxide 40%

semiconductors
used for flexible n-type This flexible composite film exhibited a response of 1.4 to
room temperature
TiO2
gas sensors 100 ppm ethanol at RT with significantly rapid response/
13%
recovery time of 5/3 s. Nanostructure of ­In2O3 octahedral
In2O3 nanopowders [69] was fabricated by oxidation of ionic pre‑
20%
cursor compound in low-oxygen atmosphere. The nanopow‑
ders were further mixed with propanediol and then deposited
on polyimide (PI) substrates. The obtained sensor exhibited
a good response of 3 to 5 ppm ­NO2 at 100 °C, perform‑
ing its great potential for FRT ­NO2 sensors. Kiriakidis et al.
[107] reported an ozone sensor based on ­InOx thin films with
Fig. 2  Schematic diagram of various pristine metal oxide semicon‑
ductor used for flexible room-temperature gas sensors introduced in cylindrical structure and nanosize grains of about 20 nm,
this chapter grown by magnetron sputtering on PET substrate. The sen‑
sor has a fabulous LOD of 15 ppb at RT and exhibited a
large response of nearly 72.5% to 15 ppb ozone.
rapid response/recovery time. Ong et al. [90] synthesized
N-type ­WO3, ­TiO2, and F ­ e2O3 were also reported for FRT
ZnO nanowires with a simple low-temperature hydrother‑
gas sensors, while other n-type pristine MOS applied for
mal method and proposed three methods, slide transfer, roll
FRT gas sensors are rarely reported. Ryu et al. [76] pre‑
transfer and thermal transfer, to transfer the samples onto
pared porous ­WO3-δ films on PI substrate with granule spray
flexible poly(ethylene terephthalate) (PET) substrates. The
process. The gas sensor exhibited high sensing properties
mechanically flexible ZnO nanowires gas sensor exhibited
with a great response of 18,500% to 10 ppm ­NO2, response/
an n-type response value of 5.0% to 1000 ppm hydrogen.
recovery time of 17/25 s and LOD of 1.88 ppm. Further‑
However, the ZnO nanowires with surface modification of
more, the sensor maintained high performance after 4,000
ammonia plasma exhibited p-type hall results, indicating
bending/relaxing cycles, showing excellent flexibility prop‑
that ammonia plasma treatment can lead to effective con‑
erties. ­TiO2 has also been reported to be used in the prepara‑
ductivity modulation of the ZnO nanowires. Furthermore,
tion of TMA sensors. TMA is known to be released in dead
the ammonia plasma-treated ZnO nanowires showed a sig‑
fishes with a pungent and ammonia-like odor. The detection
nificantly enhanced response of 15% to 500 ppm hydrogen
of ppm-levels TMA has been used to estimate the fresh‑
with no apparent degradation after 14 months long-term
ness of fishes and seafood products. However, most of the
test. Cotton fabrics have also been reported to be excellent
reported MOS-based TMA sensors work at high tempera‑
flexible substrates for MOS-based FRT gas sensors. Sub‑
ture, which is seriously inconsistent with the actual applica‑
biah et al. [104] reported a multifunctional acetaldehyde
­ iO2 nanotube prepared
tion. Perillo et al. [109] reported a T
gas sensor developed by growing hexagonal-shaped ZnO
by anodization method and then slid it onto the PI substrate
nanoparticles on cotton fabrics through seed layer enhanced
to obtain a flexible sensor. The response of ­TiO2 FRT sen‑
sol–gel techniques. The introduction of cotton fabric con‑
sor reached 150% to 400 ppm TMA with fast response time
tributes to the uniform distribution of ZnO nanoparticles
of 25 s and the detection limit was 40 ppm, meeting the
and the high porosity between yarns. More importantly, this
actual application situation. Kim et al. [71] demonstrated
ZnO nanostructure-modified cotton fabric is also equipped
a novel bio-friendly renewable N ­ O2 sensor based on cellu‑
with ultraviolet (UV) radiation protection, which reveals its
lose nanocrystals (CNC)/Fe2O3 composites, which exhibited

13
206 Page 10 of 42 Nano-Micro Lett. (2022) 14:206

whisker-shaped morphology. The CNC/Fe2O3 sensor exhib‑ RT, modification of pristine MOS materials is necessary,
ited a tremendous response of nearly 1100% to 200 ppm ­NO2 which will be discussed in the following chapters.
with fabulous reversibility, which can be contributed to the
novel dispersive morphology.
There are few p-type pristine MOS that have been reported 4 Noble Metal Nanoparticles Modified MOS
in FRT gas sensors due to their low gas response. Hübner FRT Gas Sensors
et al. [161] demonstrated that the sensitivity of the n-type
MOS gas sensor is the square of a p-type gas sensor with Surface modification with noble metals refers to doping Pt,
identical morphology, suggesting that it is a great challenge Pd, Au, Ag, and other noble metal nanoparticles on MOS
to design a pristine p-type MOS gas sensor with tremen‑ to improve the surface activity and promote the catalytic
dous sensing performance. Kuritka et al. [101] fabricated a decomposition of gas molecules, so as to make significant
fully inkjet-printed CuO-based humidity and ethanol sensor contributions to the better sensing performance [162–164].
on PET substrate. The CuO nanoparticles were fabricated Noble metal nanoparticles modification is considered to be
by microwave-assisted solvothermal method and exhibited a valuable strategy to improve the response and selectivity,
flowerlike morphology. The inkjet-printed sensor showed reduce operating temperature and response/recovery time
excellent reversibility and a great response of nearly 90% to of the MOS gas sensors [165, 166].
saturated vapors of ethanol at RT, which could be attributed
to the high surface-to-volume ratio of flowerlike-shape CuO
4.1 Mechanism of Noble Metal Modified MOS
nanoparticles. Sakthivel et al. [82] presented a FRT N ­ H3
for Enhanced Gas Sensing Performance
gas sensor fabricated by screen printing CuO nanorectangles
material on PET substrate. The CuO nanorectangles were
Surface modification with noble metals can be carried
fabricated by a surfactant-free hydrothermal method with an
out by chemical sensitization and electronic sensitization
average length and breadth of 950 and 450 nm, respectively.
[167, 168]. Chemical sensitization increases the rate of
The RT sensor showed a meaningful response to 5 ppm of
chemical processes between target gas and chemisorbed
­NH3 with response/recovery time of 90/120 s. In addition,
oxygen through the catalytic action of noble metal nano‑
the sensor exhibited tremendous stability over three months,
particles, which is conducive to the easier migration of
performing its promising application prospects. As shown
electrons, and thus enhance the performance of sensors.
above, the solely reported CuO-based p-type pristine MOS-
In chemical sensitization, the noble metal promoter acti‑
based FRT gas sensors did not perform great sensing proper‑
vates the target gas by converting it into highly reactive
ties compared to the n-type pristine MOS.
molecules and accelerating it to spill over to the semicon‑
In brief, various morphologies of pristine MOS have
ductor surface, facilitating the catalytic oxidation [169],
been synthesized and transferred to flexible substrates by
which is also referred to spill-over effect. Chemical sen‑
diverse methods for FRT gas sensors. These sensors have
sitized noble metals do not directly affect the resistance
been widely used for the detection of various gases, and
of semiconductors and its sensing mechanism is the same
some excellent sensing performance has been achieved.
as in the absence of doping. Electronic sensitization is
In particular, one-dimensional (1D) nanostructure exhibit
the exchange of electrons between noble metal and MOS
great potential to overcome high-temperature operation
surface that directly affects the resistance of MOS [168].
and low response due to their ultra-high surface-to-volume
The electronic sensitized noble metal forms stable noble
ratios and the large number of sites for adsorption of gas
metal oxides in air and are reduced to metal in a reducing
molecules, which is currently an effective strategy for
gas atmosphere [170, 171]. As the oxidation state of noble
achieving RT with pristine MOS. However, it should be
metal varies with ambient atmosphere, the state of the
noted that for most pristine MOS FRT gas sensors, their
electrons on the MOS surface changes accordingly. When
response at RT is much lower than that at higher operating
the noble metal is oxidized, an electron depletion layer
temperatures, their response/recovery time are quite long,
is established on the MOS surface, which directly affects
and sometimes these sensors cannot fully recover at RT
the resistance of the semiconductor. On the other hand,
after bending. To improve their sensing performance at

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Nano-Micro Lett. (2022) 14:206 Page 11 of 42 206

as the noble metal oxide is reduced to metal, the elec‑ related to its good crystallinity. Furthermore, the same
tronic interaction with the MOS is disrupted, resulting in group [99] also reported Ag nanoparticles modified ZnO
a decrease in the depth of electron depletion layer. These nanorods gas sensor and its optical image is shown in
electronic sensitized noble metal oxides act as receptors Fig. 3d. The sensor can be activated under visible-light
for the target gas with much stronger electronic affinity illumination: a large amount of photogenerated absorbed
than the adsorbed oxygen, enhancing the performance of oxygen ions is generated owing to the coupling between
the gas sensor [167]. Ag nanoparticles and ZnO nanorods, which results in
an increase of surface charge density and an enhance‑
ment of sensing performance. This Ag–ZnO nanorods/
4.2 FRT Gas Sensors Based on Noble Metal PI sensor exhibited a linear response to C ­ 2H2 concentra‑
Nanoparticles Modified MOS tions from 3 to 1000 ppm with the maximum response
of 26.2 to 1000 ppm ­C2H2 at 130 °C. However, the sen‑
For many noble metal nanoparticles modified MOS flex‑ sor characteristics degraded obviously after bending 1­ 04
ible low-temperature gas sensors, 1D vertically well- cycles, which might be attributed to the fracture of the
aligned ZnO nanorods are often used as the sensitive ZnO nanorods forest because of the excessive pressure.
layer due to the great inherent characteristics of ZnO and In addition, 1D nanostructures are often fabricated through
the simple hydrothermal synthesis method, for instance, the controllable electrospinning method. Featured with regu‑
Pd–ZnO nanorods/PI/PET [93], Pd–Ga–ZnO nanorods/ lated porosity, high surface-to-volume ratio, and tunable pore
PI [91] and Ag–ZnO nanorods/PI [99]. Chung et al. [93] size, the electrospun 1D nanomaterials exhibit fabulous RT
presented a FRT H ­ 2 sensor based on the Pd-decorated gas sensing properties. Moreover, modified with the proper
ZnO nanorods. Figure 3a exhibited the ZnO nanorods noble metal catalyst, the 1D nanostructured MOS gas sensors
remained vertically aligned after 1000 bending/relax‑ show better RT sensing performance. A novel n-type wide-
ing test, exhibiting fabulous mechanical flexibility. As bandgap MOS sensing material, S ­ rGe4O9 has been reported
shown in Fig. 3b, the Pd-ZnO nanorods/PI/PET sensor for the detection of N
­ H3 at RT by Huang et al. [80]. Polycrys‑
showed a large response of 91.2% to 1000 ppm H ­ 2 at RT talline ­SrGe4O9 nanotubes were synthesized via a single-noz‑
and great robustness with no significant degradation after zle electrospinning process and Pt-modified ­SrGe4O9 nano‑
­1 0 5 bending cycles with a curvature angle of 90°. The tubes were prepared by annealing the mixture of S ­ rGe4O9 and
modification of Pd nanoparticles not only enhances the ­H2PtCl6 solution, as shown in Fig. 3e. The sensing materials
sensor response, but also exhibits high selective absorp‑ were further assembled on a PET substrate to form a FRT
tion of H­ 2. The authors attributed this enhancement to sensor. The sensor exhibited a reliable detection of N ­ H3
two-factors. One is that ­H2 molecules can be easily dis‑ within the concentration of 1–500 ppm, a response of 7.08
sociated on the Pd surface: H­ 2 + Pd ↔ ­2PdHx. Second, O ­ 2 to 100 ppm ­NH3 with fast response/recovery time of 17/16 s,
in the ambient air can easily react with Pd nanoparticles excellent mechanical stability with a large bending angle of
and generate a weak-bonded state of PdO: 2Pd + ­O 2 ↔ 150° and ­103 cycles of bending/relaxing test. Pt nanoparticles
2PdO, which also can be dissociated and produce ­O2 eas‑ modified ­SrGe4O9 exhibited significantly enhanced response
ily. Furthermore, the same group [91] developed a FRT compared to the pristine ­SrGe4O9. The authors attributed the
sensor based on perpendicularly aligned ZnO nanorods enhanced gas sensing performance to electronic sensitiza‑
with Pd and Ga modifications. The Pd-3%Ga–ZnO tion and chemical sensitization. In electronic sensitization, a
nanorods/PI sensor showed excellent selective charac‑ Schottky barrier was formed between S ­ rGe4O9 and Pt, there‑
teristics towards H­ 2, as given in Fig. 3c. Beyond that, fore, the electrons transferred from S­ rGe4O9 to Pt. In chemi‑
this sensor also exhibited a large response of 91% to cal sensitization, dissociation and adsorption of O
­ 2 molecules
1000 ppm ­H2 at RT, which was improved six-fold com‑ on the surface of ­SrGe4O9 were catalytically activated by Pt
pared with the undoped Ga-seed. More importantly, this nanoparticles. The modification of noble metal nanoparticles
sensor also performed excellent mechanical stability with can also enhance the sensing properties of metal oxide-based
no degradation after bending 1­ 05 cycles, which might be heterojunction. Rh-doped 1D hollow ­SnO2 nanotubes have
also been reported for FRT ­NH3 sensors by Liu et al. [172].

13
206 Page 12 of 42 Nano-Micro Lett. (2022) 14:206

(a) (b) 1.50 (c) 100

Flat 104 times bending/relaxing H2 Undoped seed

Response, S(%) = ΔR/Ra×100%

102 times bending/relaxing 105 times bending/relaxing 1% Ga-doped seed

Relative resistance (Rg/Ra)

1.25 10 times bending/relaxing
3
10 times bending/relaxing
6
80 2% Ga-doped seed
3% Ga-doped seed
1000 800 600 400 200 100
1.00 4% Ga-doped seed
ppm ppm ppm ppm ppm ppm 60
5% Ga-doped seed
0.75 40
0.50
20
CO
0.25 CO2 N2
0
0.00 O2
100 nm 0 200 400 600 800 1000120014001600 −20 NO2
Time (s)

(d) (e) Porous Porous

Sr(NO3)2/ Sr(NO3)2/Ge(OEt)4/ SrGe4O9 Pt-SrGe4O9
Ge(OEt)4/PVP PVP nanofibers nanotubes nanotubes
solution
Electrode
PET
Add
Annealing H2PtCl6

Ag-ZnO NRs/PI Annealing

Collector

(f) (g) 6 Bend 30° NH3 Conc. 50 ppm

Response (Rg/Ra)
Initial
5 20.0k Initial Bend

4 16.0k

Resistance (Ω)
1. SnCl2/PVP nanofiber 2. Rh-doped SnO2 nanotube 3. PANI/Rh-doped SnO2 nanotube 12.0k
3 8.0k
Electrospining Sintering in air In-slu polymerization 2 4.0k

1 0.0
0 400 800 0 400 800
Time (s)
0
0 200 400 600 800 1000 1200 1400 16001800
Time (s)
6
Response (Rg/Ra)

Initial Bent for 500 times Bent for 1000 times

2
Rh
0
0 400 800 0 400 800 0 400 800
Time (s)

Fig. 3  a Cross-sectional view of the Pd-ZnO nanorods/PI/PET sensor after 1000 times bending/relaxing test. b The response, reliability test
of Pd-ZnO nanorods/PI/PET sensor. Reproduced with permission from Ref. [93]. Copyright (2013) Elsevier. c The selectivity of Pd–Ga-ZnO
nanorods/PI sensor for various Ga-assisted seed layers conditions at 1000 ppm H ­ 2. Reproduced with permission from Ref. [91]. Copyright
(2014) Elsevier. d The optical image of Ag-ZnO nanorods/PI sensor. Reproduced with permission from Ref. [99]. Copyright (2018) Springer
Nature. e Schematic illustration of the fabrication process of Pt-SrGe4O9 nanotubes. Reproduced with permission from Ref. [80]. Copyright
(2018) Springer Nature. f Schematic illustration of the fabrication process of PANI/Rh/SnO2. g Response of PANI/Rh/SnO2 sensors to 50 ppm
­NH3 at RT under bending test. Reproduced with permission from Ref. [172]. Copyright (2021) Elsevier

As presented in Fig. 3f, they synthesized Rh-doped ­SnO2 rapid thinning the depletion region of ­SnO2, resulting in a fast
hollow nanotubes by electrospinning and sintering. Subse‑ response (113 s) and larger response values (13.6 to 100 ppm
quently, the PANI coated Rh-doped S ­ nO2 hollow nanotubes ­NH3). Moreover, as performed in Fig. 3g, the response of the
was prepared by in situ polymerization and drop-coated on sensor decreases only slightly at a bending angle of 30° and
PET to form flexible sensors. Beyond that, Rh can be modi‑ it is worth noting that the bending has no significant effect
fied into the S ­ h3+
­ nO2 lattice due to the similar ionic radii of R on the initial resistance of the sensor. Even after bending for
4+
and ­Sn , which contributed to the enhanced noble metal 1,000 times, the sensor still possesses a reliable response,
sensitization. The Rh modification not only facilitates the which means that the 1D nanostructure remain stable under
adsorption of N ­ H3, but also promotes the decomposition of bending situation.
­NH3 into highly reducing H and ­NH2, which can result in a

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 13 of 42 206

In brief, modification with noble metals is also a superior 5.1 Mechanism of PANI Modified MOS for Enhanced
scheme to enhance the response and selectivity due to the Gas Sensing Performance
synergistic effect of chemical sensitization and electronic
sensitization. Noble metal modification is generally effec‑ The gas sensing mechanism of pristine PANI has been
tive in creating more defects, increasing the number of widely investigated. Among them, the most commonly
active sites, providing more oxygen species, and reducing accepted mechanism was based on the PANI protonation/
the activation energy of the reaction between the gas mol‑ deprotonation process. In the doped emeraldine salt (ES)
ecules and adsorbed oxygens, thus accelerating the dynamic form, PANI is electrically conductive and, contrarily, in the
equilibrium between oxygen adsorption and desorption. Fur‑ dedoped emeraldine base (EB) form is insulating, where
thermore, some noble metals are specific for the detection doping and dedoping can be carried out with acid or base,
of certain gases, which is beneficial for RT operation. For respectively [119]. The ability to switch between the con‑
instance, Pd-modified MOS sensors exhibit a particularly ducting and insulating forms enables PANI responsive to
large response to ­H2 due to the unique break-junction effect, acids/bases and reducing/oxidizing gases such as N ­ H3, tri‑
while Rh-modified MOS sensors have a high response to ethylamine (TEA), ­H2, ­NO2, and some VOCs.
­NH3. Beyond that, the small size of noble metal nanoparti‑ The formation of heterojunction between PANI and MOS
cles does not affect the mechanical flexibility properties of plays a significant role in the enhancement of the sensing
the sensing material. All these features help to enhance the properties. When PANI contacts MOS, the difference in
FRT gas sensing performance of MOS-based gas sensors. Fermi energy levels leads to carrier transfer, forming a het‑
erojunction and a narrow depletion region at their interface.
5 Organic Polymers Modified MOS FRT Gas When exposed to the target gas, PANI and the chemisorbed
Sensors oxygen on the surface of MOS reacts rapidly, which modu‑
lates the width of the depletion region and rapidly affects the
Organic conducting polymers-based gas sensors have resistance of the sensing nanocomposites.
attracted numerous interests due to their tunable electri‑ For instance, Quan et al. [110] synthesized network
cal properties, simple fabrication, great stability, flexibil‑ structures of PANI/SnO2 through in situ chemical oxidation
ity, environmental stability and RT operation [173–175]. polymerization. The mechanism for the enhanced sensing
However, the relatively low conductivity and the poor performance of the PANI/SnO2 composite was proposed.
selectivity restrict the application of pristine conducting When p-type PANI is in contact with n-type S ­ nO2, the elec‑
polymer-based sensors [174]. Therefore, coupling con‑ trons in S­ nO2 and holes in PANI will diffuse in opposite
ducting polymers with other heterogeneous materials is directions owing to their difference in Fermi energy levels. A
a considerable strategy to enhance the sensing properties p-n heterojunction and a narrow depletion region are formed
of the sensors [176–179]. Combing organic conducting at the interface of PANI and S ­ nO2, as presented in Fig. 4a.
polymers with MOS can complement the drawbacks of In this process, at their interface, a hole depletion region is
pristine MOS and organic conducting materials, especially formed on the surface of PANI, while an electron deple‑
the poor response and selectivity of pristine organic con‑ tion layer is formed on the surface of ­SnO2. When PANI/
ducting polymers and the high operating temperature of SnO2 is exposed to the atmosphere of the target gas TEA,
MOS [180–182]. Organic conducting polymers including on the one hand, the protons in the ­N+–H sites of PANI are
polyaniline (PANI), polypyrrole (PPy), polythiophene drawn off and PANI is reduced from the conductive doped
(PTh), poly (3,4-ethylenedioxythiophene) (PEDOT) and ES state to the insulating dedoped EB state, which leads to
polyacetylene (PA) have been widely used in fabricating a decrease in the conductivity of the materials. On the other
high-performance RT gas sensors [183]. However, only hand, the absorbed TEA molecules release electrons into the
PANI is widely used for FRT gas sensors. PANI arrested p-n heterojunction, which decrease the hole concentration of
the most interest because of its relatively high conductiv‑ PANI and the electron concentration of ­SnO2, leading to a
ity, ease of fabrication, RT operation, low cost, environ‑ thickening of the hole depletion region and a thinning of the
mental stability, and friendliness [176, 184, 185]. electron depletion region (Fig. 4a). Since the nanocomposite
exhibits p-type semiconductor behavior, the conductivity of

13
206 Page 14 of 42 Nano-Micro Lett. (2022) 14:206

(a) (b)
Wp Wa ES form PANI
Cl− Cl−
+ +
HN NH2 N N
LUMO
TEA
y H 1-y
n
Eg=2.4 eV Ev
NH3
Ef
HOMO
Eg=3.2 eV
HN NH N N
Ev y 1-y
Cl− Cl− n

p-PANI n-SnO2 EB form PANI

NH4+ NH4+

Wp-TEA Wa-TEA

TEA
Depletion layer

CeO2 CeO2
PANI-CeO2 Film
Hole Dedoped PANI Depletion region of PANI PANI NH3 PANI

conductivity pathway
Doped PANI SnO2 Depletion region of SnO2 conductivity pathway

(c) in-situ assembled on

hydrothermal dopped with Au polymerization PET substrate

InCl3·4H2O mesoporous Au-loaded mesoporous PAInxAy flexible sensing film

critric acid urea In2O3 nanospheres In2O3 nanospheres

(d) 80 (e) (f) 9

PANI PAIn10 120 PET-PAni-CoFe3O4 (50%)-50 ppm RH: 40%
Response (Rg/Ra)

PANI PAIn10
70 6
8 NH3 Conc. 10 ppm
m
Response (Rg/Ra)

PAIn10A0.5 PAIn20A1
pp

PAIn10A0.5 PAIn20A1
Response (Rg/Ra)

100

Response (Rg/Ra)
5

PAIn5A2
60 without bending 7
m

4 Initial
m
pp
b

pp

PAIn5A2
pp

bending at 60° Bending 100 times

1

50 2 80 6
0

0
m
50

10
pp

5 Bending 500 times

40 0
60
m
80

0 500 1000 1500 2000

pp

30 Time (s) 4
m

40
50
pp

3
m

20
b

pp
m

20
pp

20 2
pp
pp

10
10
0
50

1
5
1

0 0
0 1000 2000 3000 4000 5000 0
0 200 400 600 0 200 400 600
Time (s) Time (s) Time (s)

Fig. 4  Schematic illustrations of the sensing mechanism of a PANI/SnO2 and b PANI-CeO2 for enhanced gas sensing performance. Reproduced
with permission from Refs. [83, 110], Copyright (2018) Elsevier (2017) Elsevier. c The process flow for preparation of Au-In2O3@PANI sen‑
sors. d Transient response of the Au–In2O3@PANI sensors to 0.5–100 ppm ­NH3 at RT. Reproduced with permission from Ref. [79]. Copyright
(2018) Elsevier. e Response of PANI-CoFe2O4 with a bending angle of 60° at 50 ppm of ­NH3. Reproduced with permission from Ref. [84]. Cop‑
yright (2021) MPDI. f Response of PANI @ porous nanospheres S ­ nO2/Zn2SnO4 after 100 and 500 cycles of bending/relaxing test. Reproduced
with permission from Ref. [186]. Copyright (2020) Elsevier

the composite decreases rapidly and result in enhanced sens‑ a PI substrate. The nanomembranes presented a core–shell
ing properties. The mechanisms of PANI modified MOS for nanostructure with a core of ­CeO2 nanoparticles and a shell
enhanced gas sensing performance are mostly similar, and of PANI nanosheet. The author suggested that ­CeO2 nano‑
are illustrated based on the chemical state transition of PANI particles can influence the alignment of PANI and change the
and the effective electron transfer in the heterojunction. morphology of PANI shell. What’s more, an appealing dis‑
covery was observed that the synergistic oxidation of C ­ eO2
and ammonium persulfate increases the protonation and
5.2 FRT Gas Sensors Based on PANI Modified MOS
oxidation of PANI, resulting in an enhanced = ­NH+–ratio,
which would offer additional adsorption sites. Beyond that,
2D PANI nanosheets have been applied to construct the
the sensor performed a splendid gas sensing performance
core–shell nanostructures of PANI and MOS nanocompos‑
with large sensitivity of 262.7% to 50 ppm ­NH3, fabulous
ites, which can effectively enhance the sensing surface area
response-concentration linearity, great selectivity, ultralow
and electrical conductivity of the bulk of sensing materials.
detectable concentration of 16 ppb, and theoretical LOD of
­ H3 sensor based
Liu et al. [83] proposed a FRT trace-level N
0.274 ppb. In addition, there was no obvious decrease in
on in situ self-assembled PANI-CeO2 nanomembranes on

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 15 of 42 206

response after 500 times bending, which might originate ­NH3 and a significant response of 118.3% response towards
from the flexibility of polyaniline chains and the splendid 50 ppm for 24.3 s at RT. Notably, the sensor showed no
adhesion and nano-mechanical properties of PANI-CeO2 response degradation while bending at 60° (Fig. 4e) and
nanomembranes. The authors ascribed the fabulous gas exhibited a trace-level detection limit of 25 ppb.
sensing performance to the synergetic benefits of the for‑ PANI with 1D morphology was also hybridized with
mation of p-n heterojunctions and the enhanced protonation ­Fe 2O 3 to acclimatize its structural properties, forming
degree of PANI, as presented in Fig. 4b. high-performance FRT gas sensors [81, 85, 89]. Bandgar
PANI nanofibers [79, 81, 84, 87, 89, 110] and nanorods et al. [81] displayed a RT N ­ H3 sensor based on camphor
[85] usually have higher specific surface area and conductiv‑ sulfonic acid-doped PANI/α–Fe2O3 on PET substrates by
ity than the granular PANI owing to their 1D nanostructure, in situ chemical oxidation polymerization method. Camphor
which facilitates electronic interactions between sensing sulfonic acid acted as a surfactant, contributing to the dis‑
material and target gas, and endows high response and low persion of α–Fe2O3 into PANI nanofibers matrix and the
detection limit to FRT sensors. Li et al. [87] reported nano‑ generation of active sites. This flexible sensor showed an
hybrids of PANI nanofibers and flowerlike ­WO3 nanoparti‑ ultrahigh selectivity towards ­NH3 compared to liquid petro‑
cles, which was synthesized by an in situ chemical oxidation leum gas (LPG), C ­ H3OH, ­NO2, and C ­ 2H5OH. Zhu et al. [85]
polymerization method. PANI grew on the flowerlike ­WO3 prepared a sea cucumber-shaped PANI/Fe2O3 nanocom‑
surface, forming a loose and porous nanostructure, which posites by hydrothermal method, and assembled the nano‑
facilitates the adsorption and diffusion of ­NH3 molecules and composites on PET substrates. The sea cucumber-shaped
promotes the modulation of the interfacial depletion region. PANI/Fe2O3 were assembled by PANI nanorods with small
Therefore, the fabricated sensors exhibited a high response ­Fe2O3 nanoparticles attached. As the amount of precursor
of approximately 20.1 to 100 ppm ­NH3 at RT, which was ­(FeCl3·6H2O) increases, the F ­ e2O3 nanoparticles become
6 times larger than pristine PANI. What’s more, the sensor larger and the PANI nanorods become thicker. With a proper
also showed rapid response/recovery time of 13/49 s, LOD amount of precursor, the nanocomposites can have a porous
of 500 ppb, fabulous moisture resistance, great selectivity, nanostructure and a large surface-to-volume ratio, providing
and excellent mechanical stability. The same group [79] more active sites for efficient adsorption of N
­ H3. Moreover,
presented a core–shell nanostructure with the core of Au- the sensor has great reproducibility, humidity resistance, and
decorated ­In2O3 nanospheres and the shell of PANI nanofib‑ attain an excellent linear response to N ­ H3 concentrations
ers, which was synthesized by a facile hydrothermal and from 0.5 to 100 ppm at RT.
in situ chemical oxidation polymerization method (Fig. 4c). 1D PANI nanofibers were also employed to modify het‑
The fabricated nanohybrids were subsequently loaded on erostructured composites to form ternary compounds. Liu
PET substrates to form flexible sensors. The sensing perfor‑ et al. [186] achieved rapid and selective detection of N ­ H3
mance of sensors based on pristine PANI, I­ n2O3@PANI, and at RT by using in situ chemical oxidation polymerization
Au–In2O3@PANI at RT were tested as presented in Fig. 4d. method to assemble PANI@porous nanospheres S ­ nO2/
The Au–In2O3@PANI sensor showed a high response up to Zn2SnO4 nanocomposites on PET. The prepared sensor with
46 to 100 ppm N ­ H3 at RT, which is 14 and 4 times larger the optimal PANI content exhibited a large response of 20.4
than the pristine PANI sensor and I­n2O3@PANI sensor, at RT, which is 2.6 times higher than that of the pristine
respectively. The fabulous sensing properties is contrib‑ PANI (7.8) and showed a detection limit as low as 500 ppb.
uted to the chemical sensitized effect of Au, the p-n het‑ However, the response decreased by 18.99% and 26.54%
erojunction formed at the interface of I­ n2O3 and PANI, and after 100 and 500 bending cycles, respectively, as shown in
the improved protonation degree of PANI. Saleh et al. [84] Fig. 4f. To find the explanation for the decrease in sensitiv‑
presented a trace-level ­NH3 gas sensor composed of PANI ity, the morphology of the flexible sensor after 500 times of
nanofibers and C ­ oFe2O4 nanoparticles on PET substrates bending was observed through SEM. It was found that the
by in situ chemical oxidation polymerization. The n-type location of the crease bending in the center of the sensor
­CoFe2O4 nanoparticles were encapsulated in the p-type was damaged, leading to partial detachment and extrusion
PANI, forming a p-n heterojunction at the PANI–CoFe2O4 deformation of the nanocomposite. While the other parts
interface. Therefore, the sensor exhibited great selectivity to mostly preserved the primitive morphology, which makes it

13
206 Page 16 of 42 Nano-Micro Lett. (2022) 14:206

possible to achieve reliable sensing for N ­ H3 under bending ­NH3 molecules dissolved in water generated O ­ H−, which
conditions. promoted the deprotonation of PANI. Under high humidity
When PANI is used as the main component and MOS environment, these two reactions both facilitated the reaction
is used as a modifier of the sensing materials, the materi‑ degree of ­NH3 and enhanced the deprotonation of PANI,
als behave p-type characteristics acting like PANI. While which contributed to the increased humidity resistance of
constructing sensing materials with MOS as the main com‑ the PANI-based RT sensor.
ponent and PANI as a modifier is also a possible strategy to
fabricate high-performance gas sensors so that the sensing
materials exhibit the desired n-type or p-type properties act‑ 5.3 FRT Gas Sensors Based on Other Organic
ing like MOS. However, the implementation of this strat‑ Polymers Modified MOS
egy needs to depend on 0D PANI nanoparticles. Bai et al.
[111] reported a FRT TEA gas sensor by loading α-MoO3 MOS nanoparticles have been incorporated in organic poly‑
nanorods as a framework on a PET substrate and then cov‑ mers to form flexible sensing materials in recent studies,
ering the framework with 0D PANI nanoparticles through which cannot only be used as the flexible substrate of gas
in situ chemical oxidation polymerization. The formation sensors without constructing the extra substrate layer, but
of p-n heterojunctions and the porous network morphology also can optimize the gas sensing performance. Mahmoud
contribute significantly to the superior sensing performance. et al. [97] presented semi-conductive organic chitosan mem‑
The sensor performed an excellent linear response to TEA brane based flexible H­ 2S sensors. At first, W
­ O3 nanoparticles
at concentrations from 10 to 100 ppm at RT, and the LOD is were mixed with glycerin ionic liquid (IL) to form solutions.
theoretically calculated to be 0.55 ppm. What is worth notic‑ Then the homogenous solutions were cast into the organic
ing is that the negative influence of the relative humidity on chitosan sensing membrane. The presence of chitosan and
the TEA sensors is negligible. The same group [86] also pre‑ glycerol increases the content of H-bonding, accelerating
sented a heterostructure of 0D PANI nanoparticles modified the electron accommodation and transfer. As a result, the
with ­SnO2 nanofibers. The hybrid was further coated onto a fabricated gas sensors exhibited great sensing performance
PET substrate to develop a FRT N ­ H3 gas sensor. The sensor with fast response (13.6 s), a response of 2.75 to 200 ppm
reached a large response of 29 to 100 ppm N ­ H3, which was ­H2S, LOD of 15 ppm and excellent selectivity to H ­ 2S (com‑
5 and 29 times larger than the pristine PANI or ­SnO2 based pared to H ­ 2, ­NO2 and C
­ 2H2) at 40 °C. In addition, they also
sensor, respectively. fabricated two other ­H2S gas sensors based on other organic
Beyond that, PANI-modified MOS sensors also gener‑ materials [95, 96]. The flexible semiconductive polymeric
ally exhibit fabulous humidity resistance at RT. Some matrix membranes [95] were prepared by mixing carboxy‑
sensors even show increased response when the humidity methyl cellulose (CMC) powders with 5% glycerin IL and 5
increases, which is completely opposite to the conventional wt% CuO nanoparticles. The CMC/CuO/IL sensor showed a
MOS-based gas sensors. This is due to the H ­ 2O molecules response of ~ 20% to 300 ppm H ­ 2S at low temperatures with
adsorbed on the surface of PANI acting as a proton source, a detection limit of 15 ppm. Before that, they also prepared
which increases its doping level and the conductivity. Taking novel flexible membranes [96] by embedding ­WO3 nano‑
­NH3 gas sensor, which is the main subject of this chapter, particles in PVA and glycerin IL polymeric solutions. More
as an example, two reactions occur when exposed to ­NH3: importantly, the conductivity of the mentioned membrane
can be controlled by adjusting the proportion of glycerol.
NH3 + PANIH+ ↔ 𝐍𝐇+4 + PANI (5) The environmental-friendly organic materials (chitosan,
CMC, PVA) also provide a flexible matrix to accommodate
NH3 + H2 O ↔ 𝐍𝐇+4 + OH− (6) IL and MOS nanoparticles.
Hydrogel is a 3D network-structured polymeric material
­ H3 molecules adsorbed on the surface of
Primarily, the N
formed by chemical or physical cross-linking and swelling
PANI take away protons from the -NH+- of PANI to form
in abundant water [187, 188]. Recently, novel ion-conduc‑
­NH4+, and PANI changes from ES form to EB form, lead‑
tive hydrogel gas sensors have been proposed as one of the
ing to an increase in the resistance of PANI. Furthermore,
most promising flexible wearable sensors due to the tunable

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Nano-Micro Lett. (2022) 14:206 Page 17 of 42 206

sensing properties, RT operation, excellent stretchability, polymers blended with IL and MOS. The promising MOS-
transparency, biocompatibility, and facile synthesis pro‑ based hydrogel FRT gas sensor was also briefly presented.
cess [189–191]. Wu et al. [192] synthesized S ­ nO2-modified
reduced graphene oxide hydrogels ­(SnO2/RGOH) with a 3D
porous structure by simple hydrothermal process, and used 6 Carbon‑Based Materials Modified MOS
a liquid crystal polymer as a flexible substrate to form flex‑ FRT Gas Sensors
ible ­NO2 sensors with excellent mechanical bending toler‑
ance. Compared with pristine RGOH, both sensitivity and 1D carbon nanotubes (CNTs) and 2D graphene deriva‑
LOD of ­SnO2/RGOH hydrogel were improved by one order tives are emerging materials for gas sensing owing to their
of magnitude when operating at RT. The enhanced sensing high sensitivity, large surface-to-volume ratio, and abun‑
performance of the hydrogel originated from the formation dant adsorption sites [120, 193, 194]. Nevertheless, target
of p-n heterojunction at the interface of RGOH and ­SnO2, gas molecules are adsorbed on the carbon-based materi‑
which facilitated the charge transfer. In addition, the large als mainly depend on weak van der Waals forces, which
number of pores formed on 3D ­SnO2/RGOH hydrogel not restrict the high sensing performance of sensors [149]. To
only prompt the charge transfer through the charge hopping overcome the shortcomings, hybridization of carbon-based
process, but also accelerate the gas diffusion through the materials with MOS has been introduced, and this com‑
pore filling effect. Besides, numerous oxygenated groups plementary hybridization not only complements the draw‑
such as carboxyl and hydroxyl groups, which interact with backs of single components, but also introduces promis‑
­NO2 molecules through hydrogen bonding, enhancing the ing advantages [195, 196]. Recently, several reviews have
adsorption capacity of ­NO2. It is worth noting that large reported carbon-based materials modified MOS gas sen‑
mechanical deformations do not degrade the gas-sensitive sors with enhanced sensing performance [197–199]. The
performance of the 3D hydrogels due to the superior stretch‑ results suggest that the carbon-based material/MOS het‑
ability and self-healing properties, especially meet the need erostructure and the unique morphology of the composites
of flexible sensors. Technologies such as hybridization of contribute to the enhancement of the high-performance
various materials and 3D structure design will facilitate the gas sensors [200–202].
development and practical application of MOS-based hydro‑
gel gas sensors.
In brief, in this chapter, we introduced the sensing mech‑ 6.1 Mechanism of Carbon‑Based Materials Modified
anism of PANI modified MOS for enhanced gas sensing MOS for Enhanced Gas Sensing Performance
performance, which is based on the protonation/deproto‑
nation process of PANI and the enhanced sensitization of In carbon-based materials modified MOS, the main role of
the heterojunction formed at their interface. Currently, 0D MOS is to detect the target gas molecules, while carbon-
nanoparticles, 1D nanofibers, and 2D nanosheets of PANI based materials can serve as great acceptors for injected
have been employed to prepare high-performance FRT gas electrons owing to their high electrical conductivity, large
sensors of ­NH3 and TEA. Among them, 0D PANI nanopar‑ surface area and abundant adsorption sites. Although lit‑
ticles attached on MOS exhibit excellent catalytic modifica‑ tle is known about the gas sensing mechanism of these
tion. 1D PANI nanofibers usually possess better RT sensing hybrids, the data reported so far suggest that their response
performance due to better electrical conductivity and higher mechanism is based on the modulation of the heterojunc‑
surface-to-volume ratio. 2D PANI nanosheets performed tion between the MOS and the carbon-based material.
excellent mechanical stability with no degradation under In general, both CNTs and graphene derivatives exhibit
bending condition. In addition, PANI modified MOS sens‑ p-type properties. When a carbon-based material is in
ing materials exhibited fabulous humidity resistance because contact with MOS, a p–n junction or a p–p junction is
the ES to EB transition process of PANI is accelerated in formed at the interface, depending on whether the MOS
high humidity environment, expanding its application scope. material is n-type or p-type. When exposed to an oxidizing
Besides, we discussed flexible bulk materials with superior gas atmosphere, the oxidizing gas extracts electrons from
gas-sensitive properties based on other flexible organic

13
206 Page 18 of 42 Nano-Micro Lett. (2022) 14:206

the heterojunction, the interfacial potential barrier and the nanoparticles were obtained by a simple annealing process,
thickness of the depletion region increases, which ampli‑ which are attached on the surface of SWCNT bundles. The
fies the increase in resistance. However, when exposed as-grown ­Fe2O3-SWCNTs were then transferred onto PP
to a reducing gas atmosphere, the reducing gas releases plastic substrates to form flexible gas sensors, and showed
electrons to the heterojunction, the interfacial potential great mechanical robustness after large-degree deformation,
barrier and the thickness of the depletion region decreases, as shown in Fig. 5b. The fabricated F­ e2O3–SWCNTs sensors
leads to the sharp decrease of resistance. Beyond that, the obtained an enhanced response towards ­NO2, as shown in
heterojunctions can also enhance oxygen adsorption, thus Fig. 5c, and exhibited a significant response towards H ­ 2S,
forming a large number of oxygen vacancies on the surface while the pure SWCNTs sensor failed to detect ­H2S. The
of nanocomposites, providing extra active sites for sensing improved sensing performance is ascribed to the presence
reactions. of ­Fe2O3 nanoparticles, which accelerates electron trans‑
Furthermore, during the synthesis process, the carbon- port and promotes the electron–hole recombination. Gao
based material can modulate the size and morphology et al. [100] prepared flexible nylon fiber gas sensors with
of the metal oxide. Besides, the carbon-based materials SWCNTs, multi-walled carbon nanotubes (MWCNTs) and
increase the electrical conductivity of the composites, ZnO quantum dot modified SWCNTs as sensing materials.
which can transfer the electrons of sensing reactions to Remarkably, as shown in Fig. 5d, SWCNTs@ZnO exhib‑
the metal electrodes rapidly. What’s more, carbon-based ited a significant response to ethanol while the SWCNTs
materials contains a large number of mesopores, which and MWCNTs did not, which is contributed to the effect
facilitate the adsorption and desorption of gas molecules. of ZnO quantum dots. The presence of ZnO quantum dots
These will improve the sensitivity and response speed of reduces the defects of SWCNTs and decreases the charge
carbon-based materials modified MOS gas sensors. density, creating a high conductive state serves as a reduc‑
tion of the gating effect at the hybrid interface. In addition,
6.2 FRT Gas Sensors Based on CNTs Modified MOS the flexible gas sensor exhibited good mechanical bending
ability and robustness, as shown in Fig. 5e. Robustness test
CNTs is a widely used carbon-based material for gas sens‑ towards washing treatment was also conducted by wash‑
ing owing to its high specific surface area, fabulous electri‑ ing the nylon sensors for different times and the sensors
cal conductivity, and great flexibility characteristics [203]. showed no significant degradation. More importantly, the
In addition, CNTs provide an effective conductive path‑ fabricated flexible sensors were further integrated into face
way for electron transport, further improving the response masks, selectively detected N ­ H3, HCHO and C ­ 2H5OH by
value and response rate of the CNTs/MOS sensors [204]. distinguishing whether the corresponding LEDs are lighted
Single-walled carbon nanotubes (SWCNTs) are cylindrical or not, as shown in Fig. 5f.
nanotubes rolled up by honeycomb lattice carbon sheets. SWCNTs can also be easily blended with other sensing
The hybrid of SWCNTs and MOS exhibits great sensing materials to synthesize multivariate composites. Further‑
performance, especially low detection limits. Asad et al. more, noble metal nanoparticles can be easily incorporated
[112] fabricated flower-shaped CuO-SWCNTs through into various sensing materials by simple synthesized meth‑
a hydrothermal method and then the obtained materials ods such as hydrothermal, wet impregnation, and physical
were drop-casted on the RFID. As shown in Fig. 5a, the sputtering methods. Therefore, noble metal nanoparticles
obtained wireless RFID sensors can be perfectly attached are often used to fabricate ternary or even multivariate
to the skin, revealing their applications for healthcare and composites to enhance the performance of sensors [74, 79,
environmental monitoring. Beyond that, the fabricated sen‑ 205–207]. Kim et al. [74] fabricated SWCNTs decorated
sor not only selectively detected ­H2S with an ultralow LOD PdO/Co3O4 hollow nanocubes for ­NO2 sensors. PdO–Co3O4
hollow nanocubes were synthesized by calcining of Pd-infil‑
of 100 ppb at RT, but also showed a response of 35% to
trated Co-based ZIF-67. Subsequently, SWCNTs were mixed
1 ppm ­H2S with 7 s response time. Hua et al. [68] prepared
SWCNT films by floating catalytic chemical vapor deposi‑ with PdO-Co3O4 hollow nanocubes dispersed in ethanol to
help electrically bridging multiple PdO/Co3O4, which can
tion with ferrocene as the catalyst, and then twig-like F
­ e 2O 3
increase the baseline electrical conductivity. With the Pd

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Nano-Micro Lett. (2022) 14:206 Page 19 of 42 206

(a) (b) 30 0° 90° 180° 0° (c) −30 as-grown film NO2

SWNT-Fe2O3 film

Response (%)

Response (%)
20 −20

Fabricated
wireless 10 −10
Skin of sensor
hand
0 0
0 2 4 6 8 10 12 14 16 0 20 40 60 80 100
Cycle number Gas concentration (ppm)

(d) 1.4 (e) 1.3 (f)

1.3
1.2
Rg/R0

1.2
Rg/R0

1.1 1.1
SW
CNT
1.0 @Z
SW nO
CNT
ia

1.0
on

MW
e
yd

CNT
m

l
eh

0 1000 2000 3000 4000 5000

Am

no
ald

ha

Time (s)
Et
rm
Fo

Co3O4 HNCs
(g) ΔR
SWCNTs-PdO-Co3O4 HNCs NO2
(top)
cPI
(middle)

PdO
Ni/Au core-shell mesh (bottom) SWCNTs
CH

Side view Cross sectional view Magnified view (sensing layer)

Fig. 5  a The optical image of manufactured wireless RFID sensor. Reproduced with permission from Ref. [112]. Copyright (2016) Elsevier. b
Response of F­ e2O3-SWCNTs sensor under large-degree deformation. c Response of SWCNTs and F ­ e2O3-SWCNTs sensor towards N­ O2 (1, 10,
20, 50, and 100 ppm). Reproduced with permission from Ref. [68]. Copyright (2017) Elsevier. d Response of the SWCNT, MWCNT and SWC‑
NTs@ZnO nylon sensors to 500 ppm N ­ H3, HCHO and ­C2H5OH at RT. e Response of the nylon-based sensor under large-degree deformation. f
The optical image of a multifunctional mask with integrated N
­ H3, HCHO and C­ 2H5OH sensors. Reproduced with permission from Ref. [100].
Copyright (2018) Springer Nature. g Schematic illustrations of SWCNT/PdO/Co3O4 on flexible Ni/Au-PI film. Reproduced with permission
from Ref. [74]. Copyright (2017) American Chemical Society

nanoparticles modification, the hole accumulation layer on MWCNTs are concentric graphene rolled up with diam‑
the ­Co3O4 nanocubes gets thicker and accelerates the redox eters on the order of hundreds of nanometers. Unlike the
reaction with ­NO2 through the electronic sensitization. As disordered arrangement of SWCNTs, MWCNTs are ordered
shown in Fig. 5g, the SWCNTs/PdO/Co3O4 composite was and exhibit good electrical properties with enhanced charge
further integrated on the Ni/Au-PI film to construct FRT gas migration in the direction of the arrangement. The reported
sensors. Moreover, the sensor exhibited reliable detection of FRT sensors based on the hybrid of MWCNTs and MOS
­NO2 at RT with a high response of 27.33% at 20 ppm and a exhibit ultralow detection limits. Rui et al. [64] used MOFs
LOD of 1 ppm. as precursors for MOS and aligned MWCNT nanofibers

13
206 Page 20 of 42 Nano-Micro Lett. (2022) 14:206

(a) (b)
0.00
2
0.1 5
−0.01 0.2 10
20
0.4
0.6

ΔR/R
Depositing MOFs Twisting Annealing −0.02 0.8
1 ppm
MWCNT sheet −0.03 AC90
AC60
ZIF-67-Co AC30
−0.04
0 20 40 60 80 100 120
MIL-88-Fe MOFs/MWCNT sheet MOFs/MWCNT fiber MOs/MWCNT fiber Time (min)

(c) (d) (e) stra

te
0.0 0.00 2 sub
PET
5 MWCNTs WO
0.1 10 3 NP
s
−0.1 −0.01 20
0.2
20 50
0.5
−0.2 50 −0.02 1 ppm

0.5 cm
ΔR/R
ΔR/R

100

1.5 cm
−0.3 −0.03
200
−0.4 −0.04 0.7 cm
500
AC90 BC90-120°
−0.5 AC60 −0.05 BC90-60° 0.1
mm 3 cm
AC30 1000 ppm BC90-0°
−0.6 −0.06
120 130 140 150 160 170 180 0 20 40 60 80 100 Electrode
Time (min) Time (min)

Response, S(%) = (Ra−Rg)/Ra×100

Response, S(%) = (Ra−Rg)/Ra×100

24 (h) 35
Response, S(%) = (Ra−Rg)/Ra×100

(f) 14 1:1 MWCNTs-WO3NPs(S1) (g) 10 ppm WO3-MWCNTs-RGO

Unbend
103 bending/relaxing
1:3 MWCNTs-WO3NPs(S2) WO3-MWCNTs
12 1:5 MWCNTs-WO3NPs(S3)
20 30 104 bending/relaxing
Pure MWCNTs
106 bending/relaxing
5 ppm
10 16 25 107 bending/relaxing

8 12 20
6 1 ppm
8 15
4
4 10
2
0 5
0
20 40 60 80 100 120 140 0 20 40 60 80 100 120 0 5 10 15 20 25
Temperature (°C) Time (min) NO2 concentration (ppm)

Fig. 6  a The process flow for preparation of MOFs modified MWCNT fibers. Transient response of ­Co3O4/MWCNT hybrid fibers to b 0.1–
20 ppm c 20–1000 ppm ­NO2 at RT. d Transient response of the ­Co3O4/MWCNT hybrid fibers to 0.1–50 ppm ­NO2 at 0°, 60°, and 120°. Repro‑
duced with permission from Ref. [64]. Copyright (2018) American Chemical Society. e Schematic diagram of W ­ O3/MWCNT-based sensor. f
Response of W ­ O3/MWCNT-based sensor as a function of operating temperature. Reproduced with permission from Ref. [73]. Copyright (2015)
Elsevier. g Transient response of pure MWCNTs, W ­ O3/MWCNTs and W ­ O3/MWCNT/RGO. h Response of W ­ O3/MWCNT-based sensor after
different cycles of bending/relaxing tests. Reproduced with permission from Ref. [72]. Copyright (2016) Elsevier

as the conductivity path for ­NO2 sensing. First, they intro‑ transfer reactions. As depicted in Fig. 6d, the hybrid fiber
duced ZIF–67–Co into the stacked MWCNT nanosheets by sensor performed even better response when bent into dif‑
drop-casting method. Then, the MOFs modified MWCNT ferent angles, which might be ascribed to the promotion of
nanosheets were twisted and annealed in air to form ­Co3O4/ electron transfer along the straightened MWCNT fiber under
MWCNT hybrid fibers, as shown in Fig. 6a. The hybrid fiber tension. The fabricated smart textiles are also equipped with
was further sewn into commercially textile fabrics without energy storage functions, demonstrating potential applica‑
damage. The manufactured textile fabrics ­NO2 sensor per‑ tions for integrated wearable devices. Yaqoob et al. [73]
formed a broad detection range from 0.1 to 1000 ppm at mixed the prepared W ­ O3 nanoparticles and MWCNTs with
RT, as given in Fig. 6b, c. The porous MWCNT fibers help the assistance of α-terpineol, and then fabricated flexible
facilitating electron interactions and promoting electron sensors through gel casting on PET substrates, as shown

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Nano-Micro Lett. (2022) 14:206 Page 21 of 42 206

in Fig. 6e. The sensor displays an interesting phenomenon nanoparticles, increases the surface-to-volume ratio and
that the response decreases as the operating temperature accelerates electron transfer by providing more conducting
increases (Fig. 6f), which can be ascribed to the elimination channels. Graphene derivatives are also promising candi‑
or decline of the nano-Schottky barrier or p-n heterojunction dates for the exploration of high-performance carbon-based
between ­WO3 and MWCNTs at higher temperature. This gas sensors. Compared to pristine graphene and other gra‑
interesting phenomenon is contrary to the properties of MOS phene derivatives, RGO is prevailing owing to its fabulous
and informative to reduce the working temperature of MOS- characteristics such as large specific surface-to-volume ratio,
based sensors. Furthermore, they mixed reduced graphene great sensitivity, chemical and mechanical stability, and
oxide (RGO) powders into the mixture and formed a W ­ O3/ high carrier mobility. In addition to the synergetic benefits
MWCNT/RGO-based sensor on a PI/PET substrate [72]. The of MOS and RGO, the synthesis method of RGO is one
Brunauer, Emmett and Teller analysis [208] illustrated that of the most significant aspects affecting the properties of
the specific surface area of W
­ O3/MWCNT/RGO was larger the RGO/MOS-based sensor. You et al. [65] assembled a
than ­WO3/MWCNT. In addition, as shown in Fig. 6g, both ­In2O3@RGO-based 2 × 4 ­NO2 flexible sensor array by direct
­WO3/MWCNT/RGO-based and ­WO3/MWCNT-based sen‑ laser writing (DLW) process. The schematic diagram of the
sors exhibit a large response to N­ O2. The presence of W ­ O3 manufacture of the ­In2O3@RGO FRT sensors and the optical
nanoparticles not only forms a p-n heterojunction, but also photograph of the sensor array is shown in Fig. 7a, b. Confo‑
provides an efficient electron transfer pathway. As for the cal laser scanning was conducted on the border of GO and
modification of RGO, it can effectively increase the specific RGO, and the microscopy pictures is presented in Fig. 7c,
surface area and facilitate the adsorption–desorption kinetics exhibiting sharped edges that reveal the high accuracy of
to achieve better gas sensing properties. What’s more, the DLW treatment. What’s more, the surface and edges of GO
­WO3/MWCNT/RGO-based and ­WO3/MWCNT-based sen‑ sheets contain numerous oxygen containing groups (OCGs),
sors showed low detection limit of 1 and 0.1 ppm, respec‑ which makes GO insulating. After DLW treatment, the
tively. However, they both suffered from the long response resistance of I­ n2O3@GO decreased from ∼7.6 × ­108 to ~ 230
times compared with other types of MOS-based sensors. Ω due to the removal of OCGs. More importantly, DLW can
Figure 6h represents the response of ­WO3/MWCNT/RGO- also effectively promote the photoreduction of GO, allow‑
based sensor under different bending-relaxing cycles. No ing ­In2O3@RGO to be patterned on flexible substrates. The
remarkable degradation after ­106 repeated cycles, which can sensor exhibits a linear response to trace-level N ­ O2 over the
be explained by the fabulous flexible properties of MWCNTs concentration of 50–1000 ppb at RT with large response
and RGO. (31.6% to 1 ppm ­NO2) and excellent selectivity. However,
the sensor performed poorly regards to response/recovery
time (4.2/13.3 min). The great sensing performance could be
6.3 FRT Gas Sensors Based on Graphene Derivatives contributed to the recovery conductivity of GO, the p-n het‑
Modified MOS erojunctions at the I­ n2O3/RGO interface, and the formation
of nanopores on GO sheets during DLW treatment owing to
Being one of the brightest promising materials, graphene the escape of the OCGs through ­CO2, ­H2O, CO, etc.
attracted the extensive enthusiasm of researchers in the field It is known that ­WO3 has several crystalline hydrates such
of gas sensing owing to its outstanding overall characteris‑ as ­WO3·2H2O, ­WO3·H2O and ­WO3·0.33H2O. Among them,
tics, such as single atom thickness, 2D layered nanostruc‑ ­WO3·0.33H2O exhibits the best sensing performance at RT
tures, high Young’s modulus of elasticity, room-temperature [214]. Perfecto et al. [108] fabricated a FRT isopropanol
stability, large surface-to-volume ratio, and excellent ther‑ sensor based on the composite of RGO and ­WO3·0.33H2O
mal and electrical conductivity [209–211]. The synergetic nanoneedles. The RGO/WO 3·0.33H 2O composite was
effect between MOS and graphene for the enhanced selec‑ obtained by ultrasonic spray nozzle (USN) and microwave-
tivity and sensitivity of gas sensors have been well demon‑ assisted hydrothermal (MAH), as shown in Fig. 7d. The
strated [118, 212]. Goutham et al. [213] fabricated a FRT agglomerates containing ­H2WO4 with GO sheets can be
transparent LPG sensor based on CdO/graphene hybrid. converted to GO-H2WO4 clusters in a high nucleation rate
The presence of graphene reduces the aggregation of CdO by USN method, and the MAH method helps to facilitate

13
206 Page 22 of 42 Nano-Micro Lett. (2022) 14:206

(a) 1c (d) Na2WO4 + GO

m
cm coating In2O3@GO WO42− GO sheets
1 laser treatment 130 W
40 Hz
USN
Au ~35 µm GO-H2WO4
ele Breaking of
ctr droplet clusters
od micro-droplet
e
Pl s 80
ubs µm
tra
te 100
µm
In O
2
3@ GO
In O
2
3@ RG
a)
O

(b) (c) HCl

HCl (I) (II) (III)
High nucleation
rate
In2O3@GO In2O3@RGO

b) (I) (II)
MAH
160 °C, 1 h

RGO-WO3·0.33H2O

(e) 60 8 (f)
200 ppm

10 ppm
50 7 Si
NH2
(i) APTES coating (ii) GO coating NH2
1 ppm OO O
Resistance (MΩ)

6 Si
40 O OO
100 ppm

30 0 100 200 300 400 500 Cotton/elastic threads APTES-fibers GO-fibers APTES-GO
50 ppm

20
(iii) Chemical
10 ppm

(iv) APTES-ZnO coating

1 ppm

reduction
O
10 O Si NH2
O

0 250 500 750 1000 1250 1500 APTES-ZnO

RGO-fibers RGO/ZnO hybrid fibers
Time (s)

(g) 50 (h) 10.0 (i) 40

RGO Washing 0
RGO/ZnO-1 Washing 1
40 7.5
RGO/ZnO-2 Washing 3
30
RGO/ZnO-3 Washing 5
Response (%)
Response (%)

Response (%)

5.0
30 Twisted State Washing 8

2.5 20
20 Fixed End
0.0
10
10 −2.5 Free End
NO2 Dry air
0
0 −5.0
0 2 4
6 8 10 12 14 16 0 800 1600 2400 3200 4000 0 100 200 300 400 500 600 700
NO2 concentration (ppm) Twist angle (degree) Time (s)

Fig. 7  a Schematic illustration of the fabrication process for I­n2O3@RGO sensors. b The optical image of the 2 × 4 ­In2O3@RGO sensor array.
c The confocal laser scanning microscopy images of the border of GO and RGO. Reproduced with permission from Ref. [65]. Copyright (2018)
Elsevier. d Schematic illustration of the fabrication process for RGO/WO3·0.33H2O hybrids. e Transient resistance of the RGO/WO3·0.33H2O
hybrids. Reproduced with permission from Ref. [108]. Copyright (2018) The Royal Society of Chemistry. f The process flow for preparation of
RGO/ZnO hybrid threads. g Transient response of RGO and RGO/ZnO to different ­NO2 concentration. h Response of RGO/ZnO sensors under
different twist angles in 2 ppm ­NO2 (0°, 360°, 720°, 1440°, 2160°, and 3,600°). i Response versus time plot of the RGO/ZnO sensors under dif‑
ferent washing times. Reproduced with permission from Ref. [54]. Copyright (2019) American Chemical Society

the reduction of GO and form ­WO3 nanoneedles on RGO 60 to 90 s. Li et al. [54] prepared a FRT N
­ O2 gas sensor with
sheets. As illustrated in Fig. 7e, the sensor exhibited a large commercial flexible cotton/elastic threads substrates and
and linear response to isopropanol at concentrations of RGO/ZnO nanosheets as a sensing material to fabricate con‑
10–100 ppm. In addition, the response time for different ductive threads. Figure 7f demonstrated the manufacturing
isopropanol concentrations is relatively short, ranging from flow for RGO/ZnO composite threads. The introduction of

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 23 of 42 206

(a) PVDF (b) rGO

70 H2S SO2 + H2O
rGO/PVDF
60 SnO2/PVDF
rGO/SnO2/PVDF
50
Response (%)

40

30

20

10 SnO2

0
10 ppm 50 ppm 100 ppm 200 ppm 500 ppm 1000 ppm PANI

(c) 100 SnO2

10 ppm (d) 4.0 (e) 40
SnO2/PANI 5 ppm
3.5 SnO SnO /PANI
2 2 SnO /rGO 2SnO /rGO/
2
PANI
80
Resistance (MΩ)

SnO2/rGO 3.0 30

Response (%)
Response (%)

SnO2/rGO/PANI 2 ppm
60 2.5 gas
air
1 ppm
2.0 gas
air 20
gas air
40 500 ppb 1.5
200 ppb

20 1.0 gas air

10
100 ppb
50 ppb 0.5
0 0.0 0
0 500 1000 1500 2000 2500 0 200 0 200 0 200 0 200 0 10 20 30 40 50 60
Time (s) Time (s) Bending Cycles

Fig. 8  a Response comparison among the pristine PVDF, RGO/PVDF, S ­ nO2/PVDF, and RGO/SnO2/PVDF composites. Reproduced with per‑
mission from Ref. [94]. Copyright (2020) Springer Nature. b The sensing mechanism diagram of S­ nO2/RGO/PANI nanocomposites towards
­H2S. c Response comparison among ­SnO2, ­SnO2/PANI, ­SnO2/rGO and S ­ nO2/rGO/PANI. d Transient resistance of S
­ nO2, ­SnO2/PANI, ­SnO2/
RGO and S ­ nO2/RGO/PANI towards 2 ppm ­H2S. e The response of ­SnO2/RGO/PANI hybrid to 500 ppb ­H2S after bending test. Reproduced with
permission from Ref. [98]. Copyright (2019) Elsevier

APTES coating helps to strengthen the adhesion of GO coat‑ optimized ternary nanocomposites based on RGO, S ­ nO2,
ing on threads. After coating the GO film, a further chemical and polyvinylidene fluoride (PVDF) by a simple hot press
reduction reaction was performed to form RGO-threads. The method. The proposed ternary nanocomposite-based flex‑
RGO-threads were further immersed in an aqueous APTES- ible sensor showed great response of 49.2% to 100 ppm
ZnO solution and subsequently annealed to form RGO/ZnO ­H2 at RT, which is 2 and 3.5 times larger than ­SnO2/PVDF
hybrid threads. Figure 7g exhibits the response of RGO/ZnO and RGO/PVDF sensors, respectively, as shown in Fig. 8a.
hybrid threads to ­NO2, which was significantly enhanced In addition, the RGO/SnO2/PVDF nanocomposite showed
over pristine RGO sensor. Furthermore, the sensor exhib‑ excellent stability with almost no response degradation
ited great long-term stability (84 days) and low detection after being tested for a month and presented a detection
limit (200 ppb). Beyond that, the fabricated sensing threads limit up to 500 ppb. Zhang et al. [98] synthesized sub-
exhibited superior mechanical and washing durability, as ppb level FRT H ­ 2S sensors based on S ­ nO 2/RGO/PANI
shown in Fig. 7h, i. With cotton/elastic threads as the flex‑ nanocomposites. The ternary composite is closely packed
ible substrate, the sensor can even be stretched, twisted, and together in the form of a porous network structure, which
washed, providing a new perspective on wearable E-textiles helps accelerating the absorption and desorption of ­H2S, as
for practical multifunctional applications. shown in Fig. 8b. The fabricated sensor showed fabulous
RGO sheets are also excellent matrices for construct‑ sensing properties with high sensitivity (60.11% to 2 ppm
ing multivariate composites. The synergistic effect of ­H2S), response/recovery time (82/78 s), stable repeatabil‑
RGO and other multiple nanomaterials provides unprec‑ ity, and long-term stability. Figure 8c illustrates that the
edented possibilities for innovative nanostructures and high ­SnO2/RGO/PANI hybrid exhibited significantly improved
performance of gas sensors. Punetha et al. [94] prepared response compared to pristine S­ nO2 as well as the hybrid of

13
206 Page 24 of 42 Nano-Micro Lett. (2022) 14:206

­SnO2/RGO and S ­ nO2/PANI, demonstrating the superiority lamellar structure with weak van der Waals forces between
of the ternary compound. The dynamic resistance transition adjacent layers, which facilitates gas adsorption. And due
of the sensors towards 2 ppm H ­ 2S also indicated the effec‑ to the unique electrical properties, TMDCs can operate at
tive modulation of the baseline resistance by ­SnO2/RGO/ lower operating temperatures, reducing the overall power
PANI composite (Fig. 8d), which contributes to the expan‑ consumption and eliminating the need for external heating.
sion of the electronic pathway. Beyond that, the response It also has superior inherent electrical conductivity, ther‑
of ­SnO2/RGO/PANI hybrid showed no degradation after mal stability, and oxidative stability [218, 219]. However,
bending test (Fig. 8e). The reported ternary composite- the pristine TMDC-based gas sensors exhibit low and slow
based gas sensors reveal that ternary composite might help response, inadequate recovery and poor selectivity [118,
exploring a new route to develop novel FRT sensors with 220]. Therefore, promising 2D heterostructures combined
high performance, but the mechanical properties still need with TMDC and MOS have been proposed due to their inte‑
to be further studied to prevent the generation of fractures. grated advantages of both components. However, there are
In brief, this chapter presented the sensing mechanism of few papers proposed to fabricate the FRT gas sensor based
carbon-based material modified MOS sensors. Carbon-based on TMDC/MOS composites.
materials are beneficial to promote electron transfer and oxy‑ Li et al. [88] used electrospun synthesized S ­ nO2 nano‑
gen adsorption/desorption due to their high conductivity, tubes as a backbone and prepared S ­ nO2/SnS2 nanotubes
large surface area, and abundant adsorption sites. In addi‑ using an in situ hydrothermal method, and then spun-coated
tion, the heterojunction formed between the carbon-based the samples on PET substrates to form flexible sensors. Fig‑
material and MOS facilitates the rapid modulation of resist‑ ure 9a illustrates the mechanism of ­SnO2/SnS2 nanotube
ance and lower operating temperature. Moreover, both 1D in air and N ­ H3 atmosphere. The work function of S ­ nO2
CNTs and 2D graphene derivatives consist of a honeycomb- is smaller than S ­ nS2 so that the electrons are transferred
like lattice network of carbon atoms that remain resistant to from ­SnS2 to S ­ nO2. Electron depletion region and accumu‑
fracture under bending. Besides, the carbon-based materials lation region were established on the surface of ­SnS2 and
provide more conductive channels that allow carbon-based ­SnO2, respectively. When the sensor is in ­NH3 atmosphere,
material modified MOS sensors to remain responsive after gas molecules interact with O ­ −, reducing the thickness of
bending test. The potential of RGO nanosheets to construct depletion region and the resistance. The heterojunction
excellent matrices of multivariate composites is also pre‑ effect of ­SnO2 and ­SnS2 contributes to enhance the sens‑
sented. The synergistic effect of RGO, MOS, and tertiary ing performance. As presented in Fig. 9b, the S ­ nO2/SnS2
materials such as noble metals and PANI, endows to achieve nanotubes sensors showed a response of 2.48 to 100 ppm
incredible gas sensing performance. To sum up, the nano‑ ­NH3, which was almost two times higher than the pristine
composites of MOS with carbon nanomaterials have much ­SnO2 nanotubes sensors. Beyond that, the sensor presented
shorter response/recovery times, lower operating tempera‑ a relatively rapid response/recovery time of 21/110 s, LOD
ture, better mechanical flexibility, and lower detection lim‑ of 1 ppm, outstanding selectivity. More importantly, the flex‑
its than pristine MOS, although the increase in response ible ­SnO2/SnS2 nanotubes exhibited fabulous mechanically
values obtained with these nanocomposites might be less flexibility with no response decrease after bending 3,000
pronounced. times or under 150° bended angle. The fabulous FRT gas
sensing performance is attributed to the high aspect ratio
of nanotubes and the effect of S ­ nS2 modification. Kim et al.
7 TMDCs Materials Modified MOS FRT Gas [221] implemented Au–SnO2–co-modified ­WS2 nanosheets
Sensors on PI substrate. The sensor exhibited the highest response
of 3.687 to 50 ppm CO at an optimum operating voltage
Recently, gas sensing semiconducting 2D TMDCs have of 4.7 V. More importantly, the optimized TMDCs-based
aroused growing interest owing to their attractive proper‑ gas sensor exhibited fabulous sensing performance under
ties that stem from their narrow band gap, large surface area tilting, bending, and stretching conditions. As presented in
provided by the sheet-like nanostructure, and unique surface Fig. 9c, d, after 1­ 04 times bending or tilting test, the flexible
and quantum effects [215–217]. In addition, TMDCs has a sensors still exhibited a remarkable and reliable response,

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 25 of 42 206

(a) Oxygen depletion layer

depletion layer
O− SnS2
O− O− − O−
−

O− e e e
−
e− O−
SnS SnO2
e−
2
e− SnO2
O− e −
e −

e− SnO2 SnO2 e− O− SnS2

e − e−
O− e e−
−

e− e − SnS2 e− e− O−
O− O− O−
O− O
−

O− NO + H2O + e−
electron O− O−
Ec SnS2
Eg = 2.1 eV
Ef
SnO2 SnO2
Eg = 3.5 eV
hole SnS2
Ev

SnS2 SnO2
Ammonia depletion layer

(b) (c) (d)

500 ppm 6M 450
2.0 SnO2 NTs 3.9 Sensor response Res. time
Response (Ig/Ia)

@50 ppm CO, 4.7 V 3.8 Rec. time

200 400
3.7

Sensor response (Ra/Rg)

1.5 100 5M

Res. & Rec time (sec)

80
Resistance (ohm)

10 20 3.6
350
3.5
1.0 4M
3.4
0 100 200 300 400 500 600 700 300
5 3.3
Response (Ig/Ia)

SnO2/SnS2 NTs
500 ppm 3M No bending 3.2
4 1000 times 250
200 3.1
3 100 2500 times
80 2M 3.0
20 5000 times 200
2 10 2.9
10000 times
1 1M 2.8
150
0 100 200 300 400 500 600 0 200 400 600 800 1000 0 2500 5000 7500 10000
Time (s) Time (s) Number of bending (times)

Fig. 9  a The sensing mechanism diagram of S ­ H3 atmosphere. b Transient response of the pristine S
­ nO2/SnS2 nanotube in air and N ­ nO2 and
­SnO2/SnS2 to 10–500 ppm ­NH3 at RT. Reproduced with permission from Ref. [88]. Copyright (2017) The Royal Society of Chemistry. c
Dynamic resistance of Au/SnO2/WS2 to 50 ppm CO after different cycles of bending tests. d Response values and response/recovery time of Au/
SnO2/WS2 to 50 ppm CO after different cycles of bending tests. Reproduced with permission from Ref. [221]. Copyright (2021) Elsevier

which is largely derived from the high carrier mobility and ­SiO2 by CVD and transferred to a flexible PET substrate,
the layered nanostructure of ­WS2. Furthermore, for the ter‑ after which 2-nm-thick ­SnO2 was deposited on its surface by
nary compound of Au–SnO2–co–modified ­WS2 nanosheets, e-beam evaporation for ­NO2 detection. Under visible light
Schottky junctions form at the interface of Au and ­SnO2 activation, unlike the pristine M ­ oS2, which showed little
as well as Au and W ­ S2, while heterojunctions form at the variation in response to different concentrations of N
­ O2, the
interfaces of ­SnO2–WS2 and Au/SnO2/WS2, providing a functionalized ­MoS2 showed responses of 2.43, 5.84, and
large number of easily modulated heterostructures. When 7.57 at RT when exposed to 3, 6, and 9 ppm ­NO2, respec‑
exposed to CO atmosphere, the release of electrons can tively. This suggests that phototransfer of electrons at the
effectively modulate the potential barrier height of these interface heterojunction between ­MoS2 and ­SnO2 plays a
heterojunctions for rapid and high response. In addition, crucial role in the detection of target gas.
the self-heating effect endows the sensor with excellent RT In brief, 2D TMDCs are a novel gas-sensitive material
properties. When applying a voltage, the intrinsic resistance due to their unique surface effect and low operating tempera‑
­ S2 nanosheets and the numerous heterojunctions are
of the W ture. TMDCs modified MOS FRT gas sensors sufficiently
great sources of Joule heating, enabling the sensors with‑ exploit the superior mechanical flexible lamellar nanostruc‑
out additional heaters. Kang et al. [222] prepared ­MoS2 on ture of TMDCs and substantially increase the slow and low

13
206 Page 26 of 42 Nano-Micro Lett. (2022) 14:206

response of pristine TMDCs by modulating the heterojunc‑ the operating temperature. Zheng et al. [102] presented a
tion between MOS and TMDCs. Although there are few UV-activated flexible ethanol sensor through depositing
papers focus on the preparation of TMDC modified MOS ZnO nanoparticles on a PET-ITO substrate. Under UV light
FRT gas sensors, its tremendous mechanical flexibility and illumination, the sensor exhibited a large response of 2.2 to
the low operating temperature make it a promising material 800 ppm ethanol at RT. In addition, using flexible transpar‑
for FRT sensors. ent PET-ITO as a substrate, the sensor has a transmission
rate of over 62% in the visible range of 400–800 nm. As
another example, Jacobs et al. [160] reported a flexible UV-
8 Light‑illuminated MOS FRT Gas Sensors
irradiation RT ZnO sensor made of low-cost, biologically-
derived ZnS nanoparticles that can be used to effectively
8.1 Mechanism of Light‑Illuminated MOS
detect and discriminate between ­O2 and ­H2O.
for Enhanced Gas Sensing Performance
Photoactivation and molecular sieving can also be com‑
bined to achieve exclusive selectivity and large response at
Light illumination is also a superior strategy to enhance the
RT. Jo et al. [105] fabricated a monolithic FRT sensor using
gas sensing properties [223, 224], decreasing the operating
a ­TiO2 film sandwiched between a PET substrate and the
temperature of MOS gas sensor [77, 225, 226], and provid‑
ing a distinctive pathway to achieve FRT MOS gas sensors molecular sieve ZIF-7/polyether block amide (PEBA) hybrid
[227]. When the device is irradiated by light with a certain overlayer, as shown in Fig. 10a. The obtained pristine ­TiO2
wavelength, if the photon energy is larger than the MOS sensor showed an ultrahigh response to 5 ppm formaldehyde
bandgap, photogenerated electron–hole pairs will be gener‑ (Sensitivity (S) = 5,041.0) and ethanol (S = 1,1264.3) under
ated, as listed in Eq. 7. The photo-generated holes will inter‑ UV illumination (0.184 mW). In contrast, the sandwich-
act with the chemisorbed oxygen ions on the MOS surface to shaped sensor showed a large response to 5 ppm formalde‑
release oxygen, as listed in Eq. 8, leading to the decrease of hyde (S = 1350.9), while ethanol response (S = 23.5) became
the depletion region width and the bulk resistance. In other negligible, showing an exclusive detection of formaldehyde,
respects, the photo-generated electrons will interact with as shown in Fig. 10b. This result demonstrated that the
ambient oxygen molecules to form photo-induced oxygen molecular-sieving effect of ZIF-7/PEBA, successfully siev‑
ions, as listed in Eq. 9. Unlike the strong adhesion of chem‑ ing formaldehyde by ethanol filtration. The UV-irradiation
isorbed oxygen ions on the MOS surface, the photo-induced not only provided a ppb-level formaldehyde detection capa‑
oxygen ions have weak bonding with MOS and thus react bility with LOD of 3.8 ppb, but also laid a solid foundation
easily with target gas, resulting in an enhanced gas sensing for molecular sieve to improve the selectivity of formalde‑
response at RT. hyde sensor with an ultrahigh response. Furthermore, the
performance of sensors is barely affected after bending 200
hv → h+ (hv) + e− (hv) (7) times or bending at different angles. The outstanding robust‑
ness could be contributed to the superior sandwich structure.
h+ (hv) + O−2 → O2 (8) Apart from the UV illumination, visible-light illumi‑
nation assisted FRT gas sensors with improved response
e− (hv) + O2 → O−2 (hv) (9) have been presented. In particular, visible-light illumina‑
tion has attracted numerous attentions as visible light is an
environmental-friendly and easily accessible light source
for portable gas sensors. Geng et al. [70] fabricated lamel‑
8.2 FRT Gas Sensors Based on Light‑Illuminated MOS
lar layered ­ZnO1−x FRT ­NO2 gas sensors on polypropylene
(PP) substrates through suspension flame spraying (SFS)
Several FRT gas sensors under light-illuminated have been
method. The bandgap of ZnO was successfully narrowed
reported [66, 70, 75, 99, 102, 105, 160]. The pristine ZnO is
down by SFS method due to the high heating/cooling rates
a direct bandgap semiconductor with a bandgap of 3.35 eV
and reducing atmosphere. As a result, the light absorption
[228], thus it can be activated by UV-light and generate
was successfully shifted from the UV to the visible light
photo-generated electron–hole pairs to effectively lower

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 27 of 42 206

­ iO2a, pure PEBA/TiO2b, and 5MMM/

Fig. 10  a The process flow for preparation of ZIF-7/PEBA coated ­TiO2 sensors. b Gas responses of bare T
TiO2c sensors exposed to different gas with concentration of 5 ppm at RT under UV-illumination. Reproduced with permission from Ref. [105].
Copyright (2021) Springer Nature. c The linear responses of ­ZnO1−x based sensors to 0.25-1 ppm ­NO2 under white-light illumination. Repro‑
duced with permission from Ref. [70]. Copyright (2017) Elsevier. Transient response of ZI, ZIC, ZIC-L (lower g-C3N4 content), ZIC-H (higher
g-C3N4 content) sensors to 1 ppm ­NO2 at RT d in dark, e under visible-light illumination. Reproduced with permission from Ref. [66]. Copy‑
right (2021) Wiley–VCH

region. In addition, ascribed to high volume-to-surface response after being exposed to N ­ O2 and the response fully
ratio and the lamellar hierarchical porous nanostructure, the recovered to original value after removing N ­ O2. Therefore,
­ZnO1−x nanofilms showed a linear response to 0.25–1 ppm visible-light irradiation can not only effectively improve the
­NO2 under white-light illumination, as shown in Fig. 10c. In gas sensing response, but also prompting response/recovery
addition, a flexible all-inorganic RT MOS gas sensor based process.
on yttria-stabilized zirconia (YSZ)/In2O3/graphitic carbon In brief, photoactivation is effective in reducing the oper‑
nitride (g–C3N4) (ZIC) [66] was reported, employing a vis‑ ating temperature and provides a distinctive way to realize
ible-light powered scheme to lower the operating tempera‑ FRT MOS gas sensors. The mechanism of photoactivation is
ture, using fibrous ceramic YSZ as the flexible substrate and based on the activation of photogenerated electron–hole pairs
­In2O3/g–C3N4 as the activated sensing region. The promot‑ generated by the photoelectric effect. The specific preparation
ing effect of visible light on sensing performance was fur‑ process can reduce the MOS material bandgap, which shifts
ther studied. The dynamic N ­ O2 responses of YSZ/In2O3 (ZI) the light absorption from the UV region to the visible region.
and ZIC flexible sensors at RT with or without visible-light Both UV and visible light irradiation can effectively reduce the
illumination are shown in Fig. 10d, e. It can be observed operating temperature, increase the response value, and speed
that in the absence of light irradiation, the response is low up the response/recovery process, which is another perspective
and the recovery ability is negligible. In contrast, under vis‑ to achieve RT operation in addition to material design.
ible light irradiation, the sensor exhibited sharply increased

13
206 Page 28 of 42 Nano-Micro Lett. (2022) 14:206

9 Applications of the FRT Gas Sensors Based gas monitoring system can detect the lowest concentration
on MOS limit of 20 ppm. When the blue indicator light turns on,
the system is in operation. While the red warning indica‑
Gas sensors are currently used in a wide range of applica‑ tor light turns up when the N ­ O2 gas concentration exceeds
tions in smart homes, food safety monitoring, public safety, the set threshold. The N­ O2 monitoring system can also be
healthcare, medical diagnostics, environmental protection, embedded in masks and watches owing to its small volume
and industrial/agricultural monitoring. Some emerging and excellent flexibility, realizing practical applications of
applications of gas sensing include ingestible electronic flexible ­NO2 gas sensors in the field of wearable electronics
capsules, electronic skin, and smart electronic nose, impos‑ (Fig. 11a). Gao et al. [100] prepared SWCNTs, MWCNTs,
ing higher requirements on the low operating temperature, and ZnO quantum dot-modified SWCNTs as sensing mate‑
high gas sensing properties, excellent interference immunity, rials on flexible nylon fibers, which could be further inte‑
and stable mechanical flexibility of the gas sensors. Ingest‑ grated into the mask by weaving. The smart mask selectively
ible electronic capsules are non-invasive capsules that are detects ­NH3, HCHO, and ­C2H5OH by sensing the change of
delivered to the human gastrointestinal tract to detect vari‑ sensor resistance to control the corresponding LEDs to turn
ous gases such as methane, oxygen, hydrogen, and carbon on (Fig. 4f).
dioxide for human health detection [229, 230]. Gas sensors E-noses are devices used for sniffing out gaseous com‑
that exhibit high performance at RT are considered to be one pounds in the environment like the human olfactory organ.
of the key components of ingestible electronic capsules. In E-noses typically consist of numerous chemical gas sensors,
addition, the natural skin uses ion reporting signals, while which are modulated by signal and pattern recognition tech‑
the flexible, comfortable and stretchable electronic skin uses niques so that the sensor arrays can respond to a range of
electron reporting signals. The electronic skin equipped gases [232]. The selectivity is achieved by analyzing the
with stretchable gas sensors can be perfectly fitted to the characteristic patterns of response data in the sensor arrays.
human body to achieve real-time detection of environmental The integrated configuration of gas sensor arrays might be
gases. FRT gas sensors can effectively reduce the energy the future trend for constructing stable and efficient E-noses.
consumption, simplify the structure, and be applicable for Kroutil et al. [113] prepared pristine PANI, PANI/CNTs,
harsh environments, such as for the detection of flammable PANI/SnO2 and PANI/TiO2 composites on PI flexible sub‑
explosives and various low-temperature operating wearable strates. Four sensor elements were fabricated on a single
devices. The traditional MOS materials are hindered by the flexible substrate, greatly facilitating a wider and convenient
disadvantage of high operating temperature for wearable application. The expanded view, structural composition, and
applications. The MOS-based FRT gas sensors with high physical demonstration of their sensor arrays are shown in
performance presented in this paper are most attractive for Fig. 11b. The RT gas sensing performance of the fabricated
wearable device applications. Currently, MOS-based FRT gas sensor arrays towards different gas atmospheres (­ O2,
gas sensors have been reported for multi-detection sensor ­NH3, ­CO2, ­NO2, acetone, toluene, and relative humidity) was
arrays and wearable devices such as smart masks, gas sens‑ investigated. However, the sensor arrays did not further dem‑
ing watches, E-textiles, and skin-fitting RFID. onstrate effective discrimination of these gases, and the lack
With urbanization and industrialization, air pollution lev‑ of selectivity is of concern and further investigation needs
els are increasing. Monitoring of the public environment is to be carried out. It is possible to combine with machine
necessary to protect people from the gaseous pollutants and learning algorithms to achieve substantial enhancement,
toxic gases. In addition, it is significant to detect the concen‑ such as detect multiple gases and significantly improve the
tration of toxic gases in industrial production in real time and selectivity of the sensor arrays, which is unimaginable for
to develop wearable gas detection and warning devices for the traditional sensors. A sensor array consisting of pristine
workers, especially in environments where toxic gas leaks ­SnO2, ­SnO2/PANI, RGO/PANI and ­SnO2/RGO/PANI was
are likely to occur. Zhang et al. [231] deposited RGO/SnO2 carried out by Zhang et al. [98] ­H2S with different concen‑
sensing films on PI substrates by spraying process and inte‑ trations (0.1–1.2 ppm) were apparently discriminated from
grated them to form a FRT N ­ O2 monitoring system. The other interfering gas species (­ NH3, ethanol, and acetone)
processed by principal component analysis algorithm.

© The authors [Link]

Nano-Micro Lett. (2022) 14:206 Page 29 of 42 206

(a) Gas NO2-out Power light-Blue (b) Top view Bottom view
chamber

Waning
light-Red
NO2-in

Face mask

Kapton solder stop mask

Heating
element

Cu IDT Cu Temperature
electrodes electrodes sensor
Kapton Au metallization
Au metallization
layer
PANI PANI+CNT

(c) 1.0 Exhaled breath

(d) (e) Flower-shaped
(halitosis people)
Principal component 2

Exhaled breath CuO-SWCNT

0.5 (health people)
sensing material
(24.13%)

0.0

−0.5

−1.0
PANI+TiO2 PANI+SnO2
Pri −1.0 1.0
nci −0.5 0.5 t3 ZIF connector
pa
l c 0.0 0.0 nen Wearable E-textile 1 cm RFID tag
(59 ompo 0.5 −0.5 mpo 12.5 mm
o
.32 ne 1.0 −1.0 ipal c %)
%) nt c 2
1 Prin (4.7 Top view Bottom view

Fig. 11  a The FRT N­ O2 monitoring system and wearable applications for smart masks and watches. Reproduced with permission from Ref.
[231]. Copyright (2022) Springer Nature. b The expanded view, structural composition, and physical demonstration of the PANI-based sen‑
sor arrays. Reproduced with permission from Ref. [113]. Copyright (2018) IEEE. c The 3D feature space for principal component analysis of
RGO/ZnO hybrid towards different exhaled gases from healthy individuals and patients with halitosis. Reproduced with permission from Ref.
[98]. Copyright (2019) Elsevier. d The 5 × 5 gas sensors array networks of the E-textile. Reproduced with permission from Ref. [54]. Copyright
(2019) American Chemical Society. e The optical image of fabricated wireless RFID sensor. Reproduced with permission from Ref. [112].
Copyright (2016) Elsevier

Furthermore, the sensor arrays can effectively distinguish improve the reliability and expand the practical applications,
between the exhaled gas of a healthy people and the exhaled the RGO/ZnO hybrid threads were woven into a 5 × 5 sen‑
gas of halitosis patients with a detection limit of 0.1 ppm. sors array network (Fig. 11d). The response of the incor‑
The classification map is presented in Fig. 11c, where it can porated networks is close to the average response value of
be seen that the exhaled breath patterns of healthy individu‑ individual sensors, thus achieving an enhanced sensing reli‑
als are randomly dispersed, whereas the patterns of patients ability with a single measurement. More importantly, even
with halitosis are classifiable together, demonstrating its if some of the individual sensors are out of operation after
potential prospects for exhaled gas analyzers. long-term use, the network can remain in working state, thus
In smart wearable electronic devices, E-textiles are popu‑ improving the repairability, long-term stability, and prac‑
lar for their low price, light weight, and good compatibility ticality of sensor array. The wearable e-textile operating
with clothes. Li et al. [54] prepared RGO/ZnO nanosheets at RT with great sensing performance, superior flexibility
on cotton/elastic threads to form conductive sensing fibers, and scalable applications represent a novel perspective for
which are stretchable, twistable and bendable with excel‑ extensive monitoring of human activities in human–machine
lent wearability and knittability. The sensing threads exhib‑ interactions and mobile devices.
ited superior sensing performance to N ­ O2 at RT with high As the demand for low-cost, flexible, and low-energy
response (44% to 50 ppm), low theoretical detection limit wireless electronics and the growing interest in "cogni‑
(43.5 ppb) and fabulous deformation tolerance. To further tive intelligence", RFID is considered as one of the most

13
206 Page 30 of 42 Nano-Micro Lett. (2022) 14:206

revolutionary technologies to achieve ubiquitous IoTs. Asad of hazardous gases and timely alarm triggering. The per‑
et al. [112] drop-cast the prepared flower-like CuO-SWCNTs formance of MOS gas sensors can be enhanced by several
on the antenna of the commercial 13.56 MHz RFID tags methods, including preparation of various morphologies of
(Fig. 11e). The obtained wireless RFID sensor was adhered MOS, modification of MOS with noble metal, composites
with adhesive paste on the back side, which could be per‑ with organic polymers, carbon-based materials and TMDCs
fectly attached to the skin. What’s more, the RFID sensor materials, and light-illuminated assistance. The main con‑
can selectively detect H ­ 2S at RT with an ultralow LOD of clusions are summarized as follows:
100 ppb and a long-term stability of 30 days, and exhibit
excellent sensing performance under the bending situa‑ (1) Nanostructures of various morphologies for pristine
tion. These results indicates that the RT-operating mate‑ MOS have been prepared to help reducing the operat‑
ing temperature to RT and enhancing their response
rials can be manufactured into flexible RFID sensors by
value, response/recovery speed, selectivity, and LODs.
extremely facile drop-casting process, demonstrating their
Among them, 1D nanostructured sensing materials
possible wide application in healthcare and environmental (nanofibers, nanowires, nanorods, etc.) are the pre‑
monitoring. ferred materials for RT gas sensors due to their inher‑
ent geometrically higher surface-to-volume ratio. Fur‑
thermore, 1D nanostructures not only contribute to the
10 Conclusion and Future Perspectives increased adsorption capacity to the analyte, but also
provide more significant modulation of the electrical
properties when exposed to the analyte attributed to a
In this review, we have systematically analyzed and sum‑
broader region of interaction in the cross-section.
marized the recent advances on FRT MOS gas sensors. Our
(2) Modification with noble metals is also a superior
attention concentrates on the critical review of FRT gas sen‑ scheme to enhance the response and selectivity due
sors, focusing on pristine MOS and the hybrids of MOS to the synergistic effect of chemical sensitization and
modified with nanostructure noble metal, organic polymers, electronic sensitization. In addition, noble metal modi‑
carbon-based structures, and TMDCs materials. In addition, fication is generally effective in changing the surface
light-illuminated MOS-based FRT gas sensors are also sum‑ nanostructure and morphology of MOS materials,
marized. Strategies for implementing FRT gas sensors are increasing the number of active sites, creating more
defects, generating more oxygen vacancies, providing
discussed from the viewpoints of material design, alter‑
more oxygen species, and enhancing surface lattice
nate activation, and mechanism explanation. The diverse
oxygen activity. Furthermore, Schottky barriers are
types of sensors discussed above indicate that an excellent formed when noble metals are in close contact with
mechanically flexible gas sensor is the appropriate combina‑ MOS materials, which can change the electron dis‑
tion with flexible substrates (polymeric substrates, textiles, tribution and energy band structure in MOS materi‑
paper-based substrates, etc.), device structures and steady als. Moreover, some noble metals are specific for the
contact between substrates and sensing materials. At the detection of certain gases, which is advantageous for
meantime, the high-performance RT gas sensor is the justi‑ RT operation. Besides, the small size of noble metal
fied combination with morphological nanostructures, hybrid nanoparticles does not affect the mechanical flexibility
properties of the sensing material. All these processes
materials, and synergetic interfacial effect. This review will
can help to enhance the gas sensing performance of
have considerable reference value for design, fabrication and FRT MOS-based gas sensors.
development of novel FRT MOS gas sensors. (3) Organic conducting polymers especially PANI has been
Generally, MOS gas sensors have the merits of easy syn‑ widely used in MOS-based FRT gas sensors owing to
thesis, high response value, low cost, rapid response/recov‑ their tunable electrical properties, excellent mechani‑
ery, great reversibility, and excellent stability. However, their cal flexibility, RT operation, and morphological tun‑
high-temperature operation hinders their wider applications. ability. The protonation/deprotonation process of PANI
For example, when operating at RT, many MOS gas sensors and the formation of heterojunctions at the interface
of PANI and MOS endow superior sensing properties.
exhibit inadequate sensitivity, reduced selectivity and the
0D nanoparticles, 1D nanofibers, and 2D nanosheets
response/recovery process becomes slower, sometimes up
of PANI have been utilized for the preparation of high-
to tens of minutes, which is critical for the rapid detection

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performance FRT gas sensors. Among them, 0D PANI operating temperature, increasing the response value,
nanoparticles attached to MOS exhibit favorable cata‑ and speeding up the response/recovery process.
lytic enhancement. 1D PANI nanofibers show better
RT sensing performance due to better conductivity and Although tremendous advances have been made in the
higher surface-to-volume ratio. PANI nanosheets with development of FRT MOS gas sensors, many challenges
large surface area and tremendous mechanical stabil‑ and problems remain in achieving great mechanical flexibil‑
ity showed no degradation after bending tests. Beyond
ity, high response valve, rapid response/recovery, exclusive
that, the PANI-modified MOS sensing materials dem‑
selectivity, low LODs, and long-term stability. The chal‑
onstrate fabulous demonstrate resistance due to the
accelerated ES to EB transition process of PANI in high lenges and future perspectives involved in FRT gas sensors
humidity environments. Generally, organic conducting are summarized as follows:
polymers modified MOS FRT gas sensors exhibit high
sensitivity and low LODs. (a) Various MOS have been applied to FRT gas sensors,
(4) Various organic polymers such as chitosan, PVA, CMC, including n-type MOS ­(SnO2, ZnO, T ­ iO2, ­WO3, ­In2O3,
etc. are mixed with IL and MOS to form membranes, ­Fe2O3, ­MoO3, CdO, ­CeO2, ­CoFe2O4 and ­SrGe4O9), and
which can not only act as the flexible substrate, but also p-type MOS (CuO and C ­ o3O4). However, there are
exhibit gas sensing characteristics. The presence of IL still many sensitive and promising MOS that have not
can effectively control the electrical conductivity of the been applied to FRT gas sensors, such as ­V2O5, NiO,
organic–inorganic compounds and help improving the and ­MnO2, which have been extensively studied and
stretchability and flexibility of the membranes. behaved great gas sensing performance. The introduc‑
(5) Carbon-based materials including 1D SWCNTs, tion of novel MOS might be helpful to find new well-
MWCNTs, and 2D RGOs have been applied to MOS- behaved sensing materials to achieve FRT sensors.
based FRT gas sensors owing to high carrier mobility, (b) In general, most FRT MOS-based gas sensors are
unique flexibility properties, high surface-to-volume based on pristine MOS or two-component composites.
ratio, abundant adsorptive sites, and RT operation. Recently, ternary composites-based MOS gas sensors
The reported carbon-based materials modified MOS have been prepared to achieve superior performance.
FRT gas sensors typically exhibit lower LODs, shorter The substantial increase in sensing performance of ter‑
response/recovery times, lower operating temperatures, nary composites is mainly attributed to the formation
and better mechanical flexibility. However, they suffer of numerous easily modulated heterostructures at the
from the low significant increase in response value. interfaces of different components, the generation of
(6) TMDCs-modified MOS FRT gas sensors take full more defects and active sites, and the increase in pos‑
advantage of the superior mechanically flexible lamel‑ sible conducting channels. However, there are still few
lar nanostructure of TMDCs and the effective modu‑ researches focusing on ternary or multivariate compos‑
lation of heterojunction between MOS and TMDCs, ites, which may have excellent prospects for FRT gas
greatly improves the slow and low response of the sensors.
original TMDCs. However, there are few papers pro‑ (c) Flexible substrates have been developed relatively
posed to fabricate the FRT gas sensor based on TMDC/ mature at present, exhibiting great mechanical property.
MOS composite. The performance of TMDCs materi‑ Up to now, polymers (PI, PET, PDMS, nylon, etc.), tex‑
als modified MOS FRT gas sensors remains to be con‑ tiles (cotton fabric, yarn, fiber, etc.), and paper-based
cluded and discovered. substrates (cellulose, tattoo papers, etc.) have been
(7) Light illumination is an alternate strategy to realize RT widely used for flexible gas sensors. However, one of
operation. The mechanism of light illumination is based the key challenges is the cracking and spalling of the
on the activation of photo-generated electron–hole pairs sensing component. Generally, flexible gas sensors are
generated by the photoelectric effect. When illumina‑ fabricated through simple spin-coating, dip-coating,
tion, the surface of MOS generates photo-induced and drying, which leads to the agglomeration, densifi‑
oxygen ions, which have weak bonding with MOS cation, and nonuniformity of the sensing component,
and can be easily reacted with target gas, resulting in deteriorating the long-term stability and mechanically
an enhanced gas sensing performance. Both UV-light flexibility of the flexible gas sensors. As new process‑
and visible-light illumination have been employed to ing and fabricating techniques have emerged, the prepa‑
manufacture FRT gas sensors, effectively reducing the ration of flexible gas sensors has also been innovated.
Some preparation methods for in situ growth of sensing

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206 Page 32 of 42 Nano-Micro Lett. (2022) 14:206

materials on flexible substrates reported in this review configuration of gas sensor arrays might be the future
might increase the bonding between sensing materials trend for constructing stable and efficient E-noses.
and substrates, such as in situ hydrothermal process (g) Although light illumination has been demonstrated to
[92, 93], in situ sol–gel grown [104], in situ polym‑ be a useful method to enhance the performance of sen‑
erization [79, 87], and in situ self-assembly method sors, the mechanism behind it remains to be explored.
[83]. Several novel transfer methods have also been Generally, ultraviolet light sources are expensive and
reported, such as suspension flame spraying [70, 76], might lead to photodegradation of sensing materials,
hot pressing method [94], slide transfer, roll transfer, limiting its extensive applications. Therefore, designing
and heat transfer [90]. In addition, the sensing material more sensitive materials that can be activated by visible
and organic polymer solution are mixed and dispersed light is more beneficial for practical applications.
uniformly by stirring and ultrasonication, and then
solution-cast technique is used to form a monolithic To date, the development of FRT gas sensors has just
flexible sensing material [95–97, 103, 192], which is started, and there are still many challenges and issues in
beneficial for the stability and longevity. What’s more, achieving excellent flexibility and gas sensitive character‑
some specific additives such as sorbitol and glycerol
istics. In the future, as new materials, innovative processes
might be helpful to enhance the extensibility and flex‑
and advanced structures are further developed, high-per‑
ibility of the sensitive film. However, there is less
discussion on how the preparation methods affects formance FRT gas sensors will be more facilely available.
the flexible properties of the sensors, and the fracture
Acknowledgements This work is supported by This work was
mechanism of sensing films remains to be explored.
supported by the National Key R&D Program of China (Nos.
According to different sensing materials, selecting suit‑ 2020YFB2008604 and 2021YFB3202500), the National Natural
able flexible substrates to reduce the elastic mismatch Science Foundation of China (Nos. 61874034 and 51861135105),
may be beneficial to fabricate flexible gas sensors with the International Science and Technology Cooperation Program
better mechanical properties. of Shanghai Science and Technology Innovation Action Plan
(d) Up to now, TMDCs materials have been widely applied (No. 21520713300), and Fudan University-CIOMP Joint Fund
to RT gas sensors with low LODs, great response and (E02632Y7H0).
rapid response/recovery. However, it is rarely combined
Funding Open access funding provided by Shanghai Jiao Tong
with flexible substrates to form FRT sensors. TMDCs
University.
materials modified MOS might be promising materials
for FRT gas sensors. Open Access This article is licensed under a Creative Commons
(e) Owing to its good electrical conductivity, carbon-based Attribution 4.0 International License, which permits use, sharing,
materials can expand electron pathways and acceler‑ adaptation, distribution and reproduction in any medium or format,
ate electron transport when hybridized with MOS. At as long as you give appropriate credit to the original author(s) and
present, carbon-based materials modified MOS FRT the source, provide a link to the Creative Commons licence, and
gas sensors have excellent development prospects and indicate if changes were made. The images or other third party
have been reported in practical applications, such as material in this article are included in the article’s Creative Com‑
mons licence, unless indicated otherwise in a credit line to the
smart face masks, smart textiles, and wireless RFID,
material. If material is not included in the article’s Creative Com‑
which might be the earliest FRT gas sensors to be put mons licence and your intended use is not permitted by statutory
into commercial products. regulation or exceeds the permitted use, you will need to obtain
(f) At present, MOS-based FRT sensor array has been permission directly from the copyright holder. To view a copy of
reported. It is worth believing that the integrated con‑ this licence, visit [Link]
figuration of sensor array might be the future trend of
the robust flexible gas sensing system. The sensor array
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