Surfaces and Interfaces 36 (2023) 102560

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Surfaces and Interfaces

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Nanostructured metal oxide semiconductors and composites for reliable

trace gas sensing at room temperature
C.A. Betty *, Sipra Choudhury, Alpa Shah
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 85, India

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

Keywords: Nanocrystalline metal oxide thin films offer toxic gas sensing with higher sensitivity at lower temperature
Nanomaterial gas sensor compared to their bulk counter parts leading to miniaturization of the sensors, making them wearable and easily
Nanocrystalline metal oxide portable for field trials without compromising on the sensitivity, but aided with improved selectivity. Nano­
Room temperature gas sensor
material of different size, morphology, geometry, preparation methods and composition play an important role in
Toxic gas sensor
Chemiresistive sensor
sensitivity, selectivity, response time and stability of the sensor. Although there are many reports about nano­
structured materials for toxic gas sensing, they lack commercialization due to reliability issues. While some
reviews have focused on toxic gas sensors based on macro and nanostructured materials which work at elevated
temperatures and/or for a specific gas species, this review presents the systematic advances of room temperature
operating sensors and their toxic gas sensing mechanism based on design of nanostructured metal oxide semi­
conductors and heterostructures, with insights into their high sensitivity, selectivity and reliability. Recent
studies on room temperature operating trace gas sensors (for NH3, H2S, H2, NO2 and SO2) based on nano­
structured semiconducting materials and their composites in the chemiresistive mode are discussed. The roles of
nanocrystallite size, morphology, surface adsorbed species, surface charge depletion layers and heterostructure
interfaces of metal oxide semiconductors and their composite materials for reliable room temperature gas sensing
are discussed. The article concludes with current status and future scope for optimizing the nanostructures and
their heterostructure interfaces for specific gas sensing at room temperature with an understanding of the various
physicochemical properties involved in enhancing the sensitivity, selectivity, stability and commercial viability.

1. Introduction desirable accuracy, sensitivity and selectivity. Toxicity of each gas is

Due to industrial growth and use of fossil fuels, chemical compounds
and hazardous gases are released in the environment and household
areas. Trace gases are the gases that are present in small amounts in
planet’s atmosphere (0.066%) excluding the major gases such as Ni­
trogen (78.1%), Oxygen (20.9%) and their levels are increasing due to
human activities. Trace gases include carbon dioxide (CO2), methane
(CH4), sulphur dioxide (SO2), hydrogen sulphide (H2S), Ozone (O3) and
various oxides of nitrogen, ammonia (NH3) and hydrogen (H2). The
presence of unsafe levels of ammonia, hydrogen sulfide, NOx, hydrogen
and other volatile organic compounds (VOC) need to be continously
monitored by suitable modern safety system for the protection of public
health. Therefore, there is high demand for portable sensing devices
with low power consumption which are suitable for explosive environ­
ments such as in oil and natural gas, sewage and mining industries for
detecting and real time analysis of trace toxic gases and VOC with
determined by the threshold limiting values for short term exposure and
long-term exposure of these gases as decided by montoring agencies
such as Occupational safety and health administration (OSHA), WHO
[1]. The presence of some of these gases in combination is being
monitored using sensor arrays or e-nose for medical diagnosis such as in
lung cancer. Therefore, researchers are actively working in this direction
for the design and fabrication of functional novel materials and devel­
opment of software and technological procedures for providing selec­
tive, cost effective, portable/wearable, low temperature operating,
reliable and stable gas sensing systems.
In this context, many types of gas sensors such as calorimetric,
conductometric, potentiometric, catalytic, and chemiresistive types
have been employed to detect toxic gases such as H2S, SO2, LPG, various
hydrocarbons and VOC though most of them are not sensitive in sub ppm
levels, unstable or nonportable. Among them, chemiresistive type sen­
sors have been widely explored due to high selectivity, sensitivity,

* Corresponding author
E-mail address: bettyca@barc.gov.in (C.A. Betty).

https://doi.org/10.1016/j.surfin.2022.102560
Received 4 October 2022; Received in revised form 25 November 2022; Accepted 4 December 2022
Available online 5 December 2022
2468-0230/© 2022 Elsevier B.V. All rights reserved.
C.A. Betty et al.
simplicity in fabrication, compactness, lower operating temperature,
and low power consumption. Among the chemiresistive sensors, metal
oxide based sensors are widely explored because of the chemical sta­
bility, catalytic properties, earth abundance, cost effective and simple
preparation methods employed. Commercially available solid state gas
sensors are mainly based on polycrystalline metal oxide semiconductors
which are operating at relatively higher temperatures in the chemir­
esistive mode [2–4]. Though, the metal oxide based chemiresistive
sensors mainly operate at higher temperatures, many efforts have been
progressing over the years towards the development of these gas sensors
for low temperature operation. By relatively low temperature operation,
sensors operating below 50 ◦ C are considered. For polycrystalline thin
film sensors the bottleneck for room temperature operation is activation
energy required for charge carriers to cross over the dominant Schottky
diode type grain boundary barriers to reach the contact electrodes. The
potential barriers resulting from surface charge depletion layers (space
charge layers) formed on the surface of the crystallites due to the
adsorbed surface states plays a major role in increasing the sensitivity of
the sensors working in chemiresistive mode.
One of the major achievements with the onset of nanocrystalline
materials is low temperature operating, highly sensitive, portable or
wearable gas sensors as a replacement for bulky, high temperature
operating ones. Nanostructured materials offer higher sensitivity to
toxic gas due to its large surface area per unit volume, large number of
surface states and high energy of the surface states. By nanostructured
materials, structures with any external dimension in the nanoscale (1-
100 nm) or having internal structure or surface structure in the nano­
scale are included. In a polycrystalline thin film, atoms at the surface are
uncoordinated and hence surface atoms always have higher energy,
have strong molecular attraction and are easier to bond with adsorbed or
chemisorbed species, than atoms in the bulk. These advantages are
beneficial for sensing applications. This increases sensitivity, which is
predominantly a surface phenomenon, using the large fraction of surface
states available on nanocrystals for interactions with the target gas. In a
nanomaterial of few nanomerters size, about half the fraction of the total
atoms are on the surface whereas for a bulk material it is only one
millionth fraction of the total atoms that are available on the surface.
The surface states on the nanocrystal surfaces are highly energetic
resulting in strong surface reactions and faster sensor response. If we
consider metal oxide semiconductor nanostructures of few nanometer
size, the crystallites might be almost depleted of charge carriers due to
charge depletion caused by electron trapping on the surface adsorbed
species. As a result the grain boundary barriers may get reduced to re­
sistances which lead to a significant reduction in activation energy for
grain boundary barrier crossing augmented with significant change in
resistance even for very small concentrations of the toxic gas in­
teractions, leading to low temperature operation and very high sensi­
tivity [5–10]. Thus, highly active surface states and trivial grain
boundary barriers between the nanocrystals make low temperature
sensing and sensor regeneration realizable with lesser power
consumption.
A recent comprehensive review by Zhang et al. discuss about struc­
ture vs. sensing property relationships of generally used nanostructured
materials for room temperature (RT) sensing by conductometric
methods [11]. Pure Pd, Te materials, Pd based alloys and composite
materials, pure metal oxide nanostuctures, metal oxide based composite
nanostructures, organic semiconductors, organic-inorganic nano­
composite structures, various carbon-based materials etc. are discussed
for gas sensing, highlighting their sensing parameters such as sensitivity
and response time [12–18]. Current applications of low dimensional
nanomaterials in gas sensing have been reviewed by Liang et al. [17]
listing out various metal oxide nanostructures and their advantages in
sensing such as sensitivity, response time and selectivity. Joshi et al.
[18] discuss recent advances in three groups of nanostructures that have
shown remarkable potential for RT gas sensing of gases such as NOx,
NH3, H2, SO2, CO, and of vapors such as acetone, formaldehyde or
2
Surfaces and Interfaces 36 (2023) 102560
methanol. Kumar et al. report comprehensive review of the metal oxide
and 2D material based sensors for room temperature operation by
photoactivation [19]. Here we discuss nanostructured metal oxide thin
films and their composites being studied for low temperature trace gas
sensing (especially NH3, H2S, SO2, NOx, H2 etc). This review explores
the roles of structure properties such as size and shape of the nano­
structures, surface adsorbed species, charge carrier density, grain barrier
potential and interfacial space charge layer modulations of the com­
posites to their sensing parameters. Further, this article discusses reli­
ability aspects of the nanostructured metal oxide based sensors for room
temperature sensing, possibilities for preparing stable and selective
sensors, concluding with scope for their future commercial applications.
2. Role of nanostructure size and morphologies for sensing toxic
gases at room temperature
(a) Influence of surface adsorbed oxygen on conductivity of metal oxides
The electrical conductivity of the metal oxide semiconductors such
as SnO2, TiO2, WO3, ZnO, PdO etc. is decided by the surface charge on
the adsorbed surface species or surface states unlike in single crystalline
semiconductors such as Si, Ge, where doping with trivalent or penta­
valent impurities decides the conductivity. The uncoordinated or broken
bonds on the surface of metal oxides, eg: O-Sn-O on SnO2, give rise to
oxygen vacancies. In presence of air, the ambient oxygen gets adsorbed
on these oxygen vacancies due to its high electronegativity and lone
pairs of electrons. It interacts with the metal oxide surface acting as an
electron acceptor and gets ionized to form an ionic layer on the metal
oxide surface. The number of electrons gained by the oxygen (O2) during
the adsorption decides the ionic strength of the adsorbed species. In the
case of n-type metal oxides, oxygen attracts electrons from metal
forming O− , O−2 , OH species, whereas the oxygen gets ionized on the p-
type metal oxide surface forming extra holes. The type of electronic
conductivity (n-type or p-type) for metal oxide semiconductors is
decided by the mobility of electrons and holes in the material, though
both types of charge carriers are present in almost equal measure.
However, in most cases the effective mass of holes (which depends on
the curvature of the valence band) is more compared to electrons,
providing faster transport for electrons, supplemented by the capture of
electrons by the surface adsorbed highly electronegative oxygen species,
making most of the metal oxides n-type. In the case of metal oxides with
higher hole mobility, the electrostatic attraction due to the surface
adsorbed negative charges causes the positive ions/holes to be accu­
mulated in a thin layer of the surface, forming a highly conducting HAL
layer near the surface of nanocrystal and conduction occurs mainly
along the near-surface HAL. In other words, presence of the charged
surface species which depletes the charges from grain surfaces, forms
potential barriers between the grains with semiconducting grain cores in
n-type (conduction through serial paths) where as it creates the resistive
particle cores and semiconducting near-surface regions (conduction
through parallel paths) in p-type oxide semiconductors. Gas-sensing
characteristics of n- and p-type oxide semiconductors depend on the
receptor functions, conduction paths and gas-sensing mechanisms. On
target gas interaction, the surface states either donate or attract elec­
trons and the potential barriers between the grain surfaces in the case of
n-type or width of HAL layers in p-type get modified giving rise to
changes in the resistance of the film which can be monitored as a
function of the target gas concentration. Thus the chemiresistive
changes of undoped p-type oxide semiconductors towards target gases
are lower than those induced at the electron-depletion layers of n-type
oxide semiconductors though recent studies report reliable and highly
sensitive sensors based on p-type metal oxides [20,21]. Lee Jong et al.
discuss the highly sensitive and selective p-type metal oxide based gas
sensors and the role of HAL layers and structure morphologies in their
gas sensing properties [20].
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

(b) Influence of space charge layer width due to adsorbed oxygen on
various nanostructure morphologies in gas sensing
Various nanostructure morphologies such as nano particles (0D),
nanorods, nanowires, nanoribbons (1D), 2D structures such as sheets,
thin films of particles, flakes, flowers, stars, spheres and porous cubes
(3D) etc. play significant role in the high sensitivity of the chemiresistive
type gas sensors. Due to the very high reactivity of the incomplete bonds
or the fast surface states on the nanostructures, oxygen adsorption by
process of chemisorption takes place which results in passivation of
incomplete bonds. The number of highly active surface states is decided
by the size of the nanoparticle or length of nanowire and so more bonds
are likely to be passivated in the nanowire than the nanoparticle. These
bonds act as bridges for electron transfer between the gas and nanowire/
nanoparticle surface. So, the target gases are likely to form temporary
bonds in more ways with nanowire surface vacancies than with nano­
particles [22]. In the case of hollow nanorods, they possess higher
porosity and larger surface area than nanowires. Further, due to the wire
type morphological nature of the sensing system, the conduction
mechanism is no longer of a hopping type, such as the single range
hopping in polycrystalline materials or the variable range hopping in
nanocrystalline materials, but the charge carriers responsible for gas
sensing travel along a linear path [22]. This results in reduced carrier
scattering during conduction and improves the gas sensitivity of the
material.
We have already discussed that, for metal oxide nanostructures with
large number of surface adsorbed, negatively charged oxygen species,
there will be charge depletion layer formation (in n-type) /charge
accumulation layer formation (in p-type) between the nanocrystallite
grains due to the charge screening effect/electrostatic attraction. The
charge depletion layer width between the grains or the charge screening
effect between the grains due to the surface adsorbed species can be
represented by Debye length. Nanowires and nanorods with diameter of
the order of few Debye lengths have higher surface-to-volume ratio,
present faster switching between partial or complete charge depletion
upon target gas interaction, enhancing the effects of surface phenomena.
Moreover, they may be single crystalline and have well defined crystal
orientations, leading to controlled reactions and easier integration into
flexible sensors [23]. Besides, the porous or hollow rod metal oxides of
1-D possess increased surface area and provide more paths for gaseous
diffusion in a faster manner and subsequent transport of the charge
carriers unhindered towards the electrodes, which leads to sensors with
faster response and higher sensitivity [17]. Particularly response
dynamics of the 1-D materials should be faster compared to their poly­
crystalline counterpart because of lesser number of potential barriers
between the wires and unhindered transport of charge carriers produced
by surface reactions. Although single nanowire sensors have not yet
reached technology readiness, aligned nanowire sensors may be easily
integrated into flexible devices using nanocombing [24] or dielec­
trophoresis [25] techniques. Similarly, 2D nanosheets, flake like struc­
tures and layers add more surface, thus increasing the sensitivity.
Influence of size, morphology, and geometry of the nanocrystals in the
potential barrier formation are discussed in few reports [5-9,26-30].
Here in Fig. 1 we represent schematically the important points discussed
in section 2.a and b: (a) the effects of surface adsorbed species on the
carrier density and hence sensitivity (b) activation energy which influ­
ence the gas sensing response such as temperature of operation, for
various nanostructures with their size in terms of Debye length.
Fig. 1 explains the effect of surface depletion regions due to the
adsorbed surface species on various types of nanostructures, corre­
sponding potential barriers that gets formed on the surface of these
structures which gives an idea about its affects in the conductivity
characteristics and their activation energies required for sensing upon
target gas interaction. The depletion layers formed due to the surface
adsorbed oxygen species (Debey length LD) on the surface of the mac­
rocrystal grains (micrograins) of size l (top) and the concomitant change
in the carrier concentration ne at the grain boundaries (bottom) is shown
in Fig. 1a i. [7,31-35]. The depletion layer width on the surface of the
grains is the potential barrier which determines the activation energy for
the transfer of charge carriers between the grain boundary barriers.
Mostly these sensors require high temperature operation for response
and recovery. In the case of nanocrystals with size of the order of the
surface depletion width, the potential barriers between the grains are of
the order of few meV (≈ kT) making them almost like more resistive
material as shown in Fig. 1a ii (bottom) thereby facilitating the reliable
room temperature gas sensing [6,7,34,36]. Thus when the crystallite/­
grain size is of the order of LD, the charge depleted grains can switch to
highly conducting state or highly resistive state even with few number of
charge carriers exchanged by the target gas interaction, making them
highly sensitive. This fact is further explained schematically by N. Bar­
san et al. [9] (Fig. 1b) for both macrocrystals with size Xg greater than LD
and nanocrystals with Xg < LD. Here the inter grain potential barrier for
the nanocrystal grains of size Xg (< LD) is ΔeVs, which is less than kT
suggesting room temperature operation while for larger grains eVs is
quite significant. Small NP film (bottom) has good contacts among the
NPs, leading to abundant parallel conducting channels and higher

Fig. 1. a Schematic representation of space charge layers at the surface of (i) microgranular film (grain size, l > 2LD, where LD is Debye length) and (ii) nanogranular
film (grain size, l < 2LD) with their corresponding charge carrier densities ne and change in carrier densities Δne at the grain boundaries (lower part of (i) and (ii)),
copy right [31]. b Schematic representation of microgranular film (grain size, Xg > LD) (top) and nanogranular film (grain size, Xg < LD) (below) with their cor­
responding barrier energy Eb and potential eΔVs. The barrier potential at the nanograin boundaries, eΔVs < kT for nanogranular film results in flat band condition, i.
e., without any significant barrier potential between grains [9]. c Influence of wire/rod length (l) and wire/rod diameter (D) on the carrier density of wire/rod
boundaries in a nanowire film (i) and microwire film (ii). d Schematic of p-type metal oxide grain interface (top) with insulating core and conducting HAL near the
surface, and their corresponding charge carrier concentrations (bottom), copy right [20].

3
C.A. Betty et al.
Fig. 1. (continued).
current signal whereas the big cluster film (top) has much less effective
contacts among the grains leading to less conducting channels and lower
conductance. Similary nanowires and nanorods also can have switching
from high conducting state to low conducting state depending on
whether their daimters D are ≤ LD. Fig. 1c shows the ideal case of
aligned nanowires with the influence of wire/rod length l and diameter
D on the carrier density at wire/rod boundaries. From the figure it is
clear that the conducting channel is thinner for the nanowire (Fig. 1c i)
compared to the microwire (Fig. 1c ii) facilitating significant changes in
carrier density for the former with target gas interaction. Thus, in gen­
eral it can be presumed that the magnitude of the potential barrier be­
tween the grains to electronic conduction strongly depends on the ratio
of the grain size/wire diameter (D) to the depletion layer thickness (LD)
[34]. In the upper part of Fig. 1 d, the schematic of two p-type micro­
grains with adsorbed oxygen species are shown, which attracts electrons
from the metal atoms. Highly conducting HAL layer on the surface of
4
Surfaces and Interfaces 36 (2023) 102560
nanocrystal and resistive core for p type metal oxide film with corre­
sponding carrier concentrations are shown in the bottom of the figure
[20]. Asadzadeh et el. [37] have modelled the gas sensor response of a
nanowire showing the dependence of surface charge on the nanowire
surface interactions with ambient gas. The response model allowed the
authors to simulate the sensor response of the nanowire using numerical
solution of the Poisson-Boltzmann equation for the electrostatic poten­
tial in cylindrical geometry. Simulations showed saturation in depletion
length λ versus surface charge density σ which leads to the conductivity
decrease with increasing surface charge density. Thus, saturation in
depletion width limits the diameter of the nanowire/rods for higher
sensitivity.
(c) Nanostructure material synthesis for gas sensing applications
The morphology of the nanostructures depends on the method,
C.A. Betty et al.
Fig. 1. (continued).
precursors, pressure and temperature etc. used in the synthesis. Various
methods such as self assembly, electrochemical, hydrothermal, chemical
co-precipitation, chemical and physical vapour deposition, sputtering,
atomic layer deposition, successive ionic layer deposition, spray pyrol­
ysis and molecular beam epitaxy are used for preparing nanostructured
materials, thin films and heterostructures used for trace gas sensing.
Atomic layer deposition, sputtering and molecular beam epitaxy (MBE)
and Langmuir Blodgett (LB) technique provides films with close packed
and uniform size nanocrystallites or grains. Uniform size of the grains
reduces the interface energy and hence reduces the ion migration effects
between the grains increasing the electrical stability of thin films.
Atomic layer deposition and MBE requires sophisticated instruments
with high vacuum whereas sputtering requires large amount of the
precursors for the targets. Templating to get uniform crystal size have
advantages, however, high temperature heating to remove the templates
may affect the size uniformity of the particles. Among the various self-
assembly methods, LB technique offers deposition of nanocrystalline
inorganic materials (SnO2, TiO2, PdO and WO3) in the form of thin films
with very precise thickness control [31,33,34,21,38,39] without any
high vacuum requirement. Hence, LB method is a viable technique
which provides films with reproducible sensing parameters and better
stability. Electrochemical methods also offer preparation of microporous
silicon (PS) and polyaniline thin films offering consistent performance
for gas sensing studies [34]. Electrochemical methods offer very good
control of pore size in porous structures and thickness of thin films and it
is cost effective. Chemical precipitation methods were used for prepar­
ing porous ZnO nanoparticles and subsequent impregnation in PS results
in heterostructures for highly selective NO2 sensing [40]. Drop casting,
spin coating and dip coating of chemically or hydrothermally syn­
thesised nanomaterials in the form of thin films are cheaper techniques,
however, the reproducibility of the baseline parameters of the devices
for long term use can be an issue. Scope of the review does not permit
elaboration of material preparation methods for different morphologies,
however, Table 1-5 gives a list of the nanostructured metal oxides and
composites prepared by various methods and their trace gas sensing
properties. Though some of these methods offer good control on nano­
structure size, morphology and flexibility to make thin films, hetero­
structure or composite films which provide very high gas sensitivity at
room temperature, the choice of the synthesis methods would be
decided by the cost effectiveness, reproducibility, large scale production
feasibility and material response stability.
5
Surfaces and Interfaces 36 (2023) 102560
3. Nanocrystalline thin films of metal oxide semiconductors for
room temperature toxic gas sensing: sensor response, sensitivity
and selectivity
Sensor operation temperature, sensitivity, selectivity, response and
recovery time are the key components of thin-film gas sensors that are
crucial for employing them as commercially viable sensors. These pa­
rameters are mainly dependent on effective surface area, defect density,
additives, and crystal structure of the sensing layer and target gas
properties. Table 1-5 gives summary of the extensively studied nano­
materials and composites which are recently reported for sensing 4
major trace gases (H2, NO2, SO2 and NH3) and one industrial emission
gas (H2S) at room temperature and the dependence of the material
morphology and synthesis methods for highly sensitive and selective
room temperature sensing. These gases are encountered by humans in
day-to-day life. These tables also give the gas sensor specifications such
as sensitivity, response and recovery time, limit of detection (LOD) and
their corresponding references. Response of the sensors were calculated
in different ways and labelled in table as: a, b, c, d, e, where Ra: resis­
tance of the sensor exposed to the reference gas, Rg: resistance of the
sensor exposed to the target gas. Among these sensors promising struc­
tures and/or composites with better sensor specifications would be
further discussed for each type of gas detections.
3.1. Nanostructured materials for room temperature operating NH3
sensor
Ammonia (NH3) is a colorless and poisonous gas, which is used as a
compound fertilizer in agriculture, synthetic fibre, biofuel, surfactant,
pharmaceutical and dye manufacturing industries. Inhalation of
ammonia may cause chronic lung diseases while excessive deposits to
ecosystems may result in nutrient imbalances and eutrophication. OSHA
has set a 15 min exposure limit for gaseous ammonia by a volume of 35
ppm in environmental air. Table 1 shows the materials studied and their
gas sensing specifications for NH3 [31-33,41-72].
For metal oxide semiconductors, sensing effects are determined by
the capability of the metal ions to change their valence state upon
oxidation/reduction. The electrochemical activity of different target
gases determines the interaction with the surface adsorbed oxygen
species. Strong reducing gas takes away the adsorbed oxygen species
releasing electrons to the conduction band of n- type metal oxide [12,
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

Table 1
Room temperature operated NH3 sensor [a = Ra/Rg; b = ΔR/Rg: b1 = Ra-Rg/ Ra; c = ΔR/Rg x100%, d = ΔR /Ra x100%; e = Ra/Rg x 100%].
Sr. Nanomaterials studied for Synthetic method Morphology Sensitivity details LOD Ref. no.
No NH3 sensors Conc. Response tres(s) trec(s) ppm
ppm

1. Nanocrystalline SnO2 LB method nanoparticles 5 15 d 10 100 5 [32, 33]

2. Porous In2O3 layer-by-layer assembly on CNT nanotubes 20 2500 a <20 <20 5 [31]
templates
3. 3D Hierarchical porous PS spheres templated transformation Quasi-spherical 100 146 b1 2 - 0.5 [41]
Co3O4 route
4. ZnO thin films spray pyrolysis spherical grains 25 233 a 20 25 5 [42]
5. ZnO thin films dc magnetron sputtering ball-like 100 304 a 92 113 5 [43]
6. TiO2 hydrolysis quantum dot clusters 0.2 2.13 a 88 23 0.2 [44]
10 7.8
7. TiO2 film functionalized with sol–gel porous 50 35 d 240 360 10 [45]
the cyanidin dye.
8. TiO2 .EMIM-PF6 sol–gel nanoparticles 100 10080 a 35.5 59 1 [46]
9. Pd/TiO2 Electrospinning Nanofiber 100 6.97 a 3 150 0.1 [47]
10. CuO flexible hydrothermal nano rectangles 5 0.25 b 90 120 5 [48]
11. Nanocrystalline CuO surfactant assisted sol-gel auto facets like- weakly 100 0.99 b 30 - [49]
combustion aggregated clusters
12. Nanocrystalline CuO sol-gel auto combustion route with cetyl spherical nanoparticles 100 9.83 b 150 500 [50]
tri methyl ammonium bromide.
13. VO2/CNT nanocomposites hydrothermal Nanoparticles on 45 0.04 b 290 1800 0.02 [51]
nanotubes
14. SnO2/rGO hydrothermal nanorods 200 1.3 a 8 13 20 [52]
15. TiO2/rGO hydrothermal microspheres 30 3.5 c 600 600 5 [53]
16. Cr2O3 activated ZnO thick screen-printing 300 13.7 b 25 75 [54]
films
17. NiO/ZnO hydrothermal nanocones 50 42 c 27 150 15 [55]
18. CuO/TiO2 sol–gel nanoparticles 50 97 c 2 55 5 [56]
19. CuO/MnO2 hydrothermal flowers/sheets 100 135 d 120 600 20 [57]
20. Silica/CeO2 hydrothermal nanoparticles 80 3244 c 750 - 0.5 [58]
21. rGO-CuFe2O4 nanocomposite solution combustion 5 2 3 6 5 [59]
200 25 d
22. Pd/SnO2/rGO chemical solution. nanoparticles 5 7.6 d 420 3000 5 [60]
23. Pd/TiO2/rGO one-pot polyol Nanoparticles/nanorods 50 14.9 d 184 81 2.4 [61]
24. SnO2/MWCNTs microelectronic Nanoparticles/fibres 200 26 a <300 300 40 [62]
nanocomposites
25. graphene-SnO hybrid film CVD followed by thermal oxidation Sheets 50 21 d 15 30 5 [63]
26. ZnO /CNT flame transport Tetrapodal- networks 100 330 a 18 35 0.2 [64]
27. Nanohybrids of 2D WS2 sonochemistry nanosheets /QDs 250 43.7 d 200 ~174 20 [65]
/TiO2
28. Sn-TiO2/rGO/CNT solvothermal nanoparticles 250 85.9 d 99 66 25 [66]
nanocomposite 25 17 d
29. WO3/rGO ultrasonication nanospheres 10 4.5 b1 18 24 1.14 [67]
100 15
30. ZnO–rGO hydrothermal Nanowire 1 24 d 180 150 1 [68]
31. PbS/TiO2 successive ionic-layer adsorption QDs/ nanotube 100 17.49 a - - 2 [69]
32. SnO2@ Polyaniline hydrothermal and in-situ 100 29.8 a 125 167 0.01 [70]
nanocomposites polymerization.
33. ZnO-NPs/MEMS chemical 1 39.7 d 0.1 [71]
0.4 21
0.3 17
0.1 6.9
34. N-GQD coated hollow In2O3 electrospinning and calcination nanofibers 1 ppm 15.2 a 0.6 [72]

13]. Electrons released from the surface adsorbed oxygen species on
interaction with these gases increases the number of charge carriers
resulting in the current increase. Similarly, strong oxidizing gases traps
conduction band electrons decreasing conductivity. Though most of
n-type metal oxides show increase in current on interaction with weak
reducing gas such as NH3 with reaction products such as N2 or NO and
electron release to conduction band, few have shown decrease in con­
ductivity suggesting a complex kinetics at room temperature which is a
function of the electronegativity of the metal oxide surface, crystallite
size, change in the carrier concentration and effects on carrier mobility.
Porous In2O3 nanotubes prepared on CNT template using layer by
layer assembly method [31] with ultrahigh surface-to-volume ratios
showed high sensitivity to NH3 at room temperature with high repro­
ducibility. Sensors based on ZnO thin films prepared by spray pyrolysis
and DC magnetron sputtering showed higher sensitivity for NH3 sensing
at room temperature [42,43]. ZnO is an n-type semiconducting oxide
with band gap of ~3.5 eV and it showed increase in current with NH3
gas [42]. Annealing carried out on films deposited by spray pyrolysis
showed uniform spherical morphology of the crystallites. These sensors
showed high sensitivity, selectivity and reliability with repeatable
measurements over 12 days towards NH3 exposure, with 2% variation in
sensitivity with humidity variation. DC magnetron sputtering provided
uniform formation of a rugby ball-shaped ZnO nanostructure [43].
Highest sensitivity with fast response and recovery times for NH3 with
selectivity is reported for n-type TiO2 samples with the highest anatase
phase percentage prepared by addition of ionic liquid 1-ethyl-3-methy­
limidazolium hexafluorophosphate [EMIM⋅PF6] in porous polysulfone
membrane [46]. These sensors showed stable response over a period of 8
months. Among the three crystalline phases of TiO2, namely anatase (3.2
eV, tetragonal), rutile (3.0 eV, tetragonal) and brookite (orthorhombic),
anatase phase shows better gas sensing due to its higher crystallinity,
higher carrier mobility and adsorption sites for the gases than rutile

6
C.A. Betty et al.
phase. One dimensional ordered porous Pd@TiO2 nanofibers array film
prepared by one-pot synthesis of electrospinning approach showed high
sensitivity with increase in current for NH3 exposure and stable response
for 5 weeks [47]. In Pd/ TiO2 nanocomposite, Pd NPs on the substrate of
TiO2 was suggested to be sensitive to NH3 due to the generation of acid
sites which can greatly improve the NH3 adsorption-desorption ability.
Sakthivel et al. reported flexible copper oxide (CuO) sensor capable of
sensing NH3 of concentrations as low as 5 ppm [48]. CuO is a p-type
metal oxide with a narrow bandgap of 1.4 eV. SnO2-rGO [52] and
TiO2-rGO [53] synthesized by simple hydrothermal method are sensitive
to NH3 at RT, but response and recovery time are poor in TiO2-rGO films.
Graphene oxide (GO) is an oxidized form of highly conducting graphene
and is more resistive where as in reduced graphene oxide (rGO), most of
the oxidized groups are removed during reduction but some oxide
groups remain in the structure which limits electron flow in the sheets.
The high surface area of rGO provides better adsorption on the surface
especially for polar gas molecules such as NH3.
Incorporation of WO3 (n- type, bandgap < 3 eV) into 2D rGO
structures (Fig. 2, top) provides a greater number of reactive sites and
the voids in the graphene sheet may provide excellent permeability to
NH3 due to physisorption for selective and sensitive detection of NH3
[67]. rGO behaves like p-type with excess holes (Fig. 2, bottom). p–n
heterojunction and ohmic contact play important roles in the enhance­
ment of sensor performance towards NH3 detection. Though oxygen is
removed by NH3 from the composite surface forming NO and H2O (Fig. 2
bottom), the rGO/WO3 composite showed p-type behavior with increase
in resistance which may be due to dominant effects of rGO. rGO pos­
sesses a higher work function and more defects in the prepared nano­
composite surface, which will provide many adsorption centers for NH3.
SnO2/ polyaniline (PANI) nanocomposites show enhanced sensing
Fig. 2. a Schematic representation of rGO/WO3 nanocomposite formation using the ultrasonication method. b Reproducibility of 5% rGO/WO3 on exposure to NH3
(60 ppm) at room temperature. c Its gas sensing mechanism towards NH3 at RT. Published by The Royal Society of Chemistry [67].
7
Surfaces and Interfaces 36 (2023) 102560
performance which was attributed to the micro-structure with large
specific surface area and the formation of p-n heterojunctions at the
surface between PANI and SnO2. The gas sensing mechanism was related
to the resistance change in the protonation /deprotonation process.
Hydrochloric acid doped polyaniline (PANIH+) has a polarized and
di-polarized structure and thus exhibits good electrical conductivity.
When the sensor was exposed to NH3, NH3 capture the proton from
PANIH+, converting PANI from conductive emeraldine salt to
non-conductive emeraldine base [70]. Thus, from above discussions, it
can be observed that work function of the material, porosity,
morphology, composition of the material, specific surface area and
heterojunction properties etc. are responsible for ultrasensitive toxic gas
sensing and response-recovery properties at RT. PANI/Nitrogen
doped-Graphene Quantum Dots (GQD)/hollow In2O3 nanofiber ternary
composites showed high sensitivity towards NH3 due to the increased
surface area and heterojunction effects [72].
3.2. Nanostructred materials for room temperature operating H2S sensor
Hydrogen sulfide (H2S), as a commonly used chemical gas is exten­
sively utilized in metallurgy, medicine, pesticide and catalyst fields. H2S
is prevalent in oil and natural gas industry, sewage disposal and in
mines. It is a colorless, flammable, an irritant and toxic gas, which can be
harmful to the human nerve and respiratory system even at low con­
centration and at higher concentration > 50 ppm, one may lose the
ability to sense the gas. Exposure limit of H2S for short term (10 min) and
long term (8 h) has been set to 15 ppm and 10 ppm, respectively. Table 2
for lists the materials studied for H2S sensing [33, 73-98].
On interaction with H2S, n-type metal oxides show increase in con­
ductivity with reaction products SO2 and release of electrons to metal
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

Table 2
Room temperature operated H2S sensor [a = Ra/Rg; b = Δ R/Rg; c = Rg – Ra /Ra X 100%; d = Ig/Ia × 100; e= (Ig − Ia)/Ia × 100%].
Sr. Nanomaterials studied for H2S Synthetic method Morphology Sensitivity details Ref. No.
No. sensors
Conc. Response tres trec(s) LOD
ppm (s) ppm

1. Nanocrystalline SnO2 LB method nanoparticles 1 25 c 30 300 0.5 [33]

2. Porous α-Fe2O3 hydrothermal nanoparticles 100 38.4 a ~180 3700 0.05 [73]
3. ZnO colloidal quantum dots 50 113 a 16 820 10 [74]
4. Porous Cu-In2O3 solvothermal colloidal quantum dots 5 90 a 72 200 0.5 [75]
5. ZnO vapour phase transport nanorods with flower- 1 296 a 320 3592 1 [76]
like structure.
6. ZnO vapor-phase transport dendrites 100 17.3 a ~15 ~30 10 [77]
7. ZnO hydrothermal nanorods 0.05 1.7 a - - 0.05 [78]
8. ZnO CVD Combs 4 6a 22 540 0.1 [79]
9. Au sensitized/ZnO vapor transport Nanorods with flower 3 475 a 660 1200 0.5 [80]
like st.
10. CuO/ZnO pulsed laser deposition Nanoparticle/ nanorods 0.5 25 e 180 15 0.5 [81]
11. CuO biotemplate biomorphic tubes 5 41 a 29 41 0.002 [82]
12. In2O3 carbothermal whiskers 10 30 c 60- 7200 0.2 [83]
240
13. In2O3 electrospinning nanotube 50 320 a 45 127 [84]
14. Porous In2O3 electrospinning nanotubes 20 166 287 636 [85]
15. CeO2 Hydrothermal Nanowires 0.05 1.11 24 15 [86]
16. Au/ZnO hydrothermal nanowires 5 79.4 a - 170 1 [87]
17. CuO thin films oxidation of Cu films well facetted grains 5 250 c 60 90 0.1 [88]
18. Sb/SnO2 thermal evaporation nanoribbons 100 18 a 500 500 0.1 [89]
19. CuxO:SnO2 thin film spray method Nanoparticles/nanorods 0.5 10 c dry 21 204 0.5 [90]
air
20. Cu2O/Co3O4 of heteroarrays by 2D electrodeposition nanowires/bamboo 20 2600 d 100 100 0.1 [91]
shape
21. SnO2 /CuO heterojunctions screen printing /dipping Thick film/grannular 1 3672 b 15 240 on 10 [92]
heating
22. CdS /Co3O4 microspheres in situ growthmethod quantum dots / ultrathin 100 12.7 a 0.6 1.0 1-5 [93]
porous nanosheets
23. CuO/MoS2 Hydrothermal /layer-by- Nanorods/ nanosheets 30 61 c 26 18 0.5 [94]
layer self-assembly
24. Graphene quantum dot Spin coating/magnetron quantum nanoparticles/ 0.1 15.9 14 13 0.025 [95]
functionalized porous and sputtering nanosheets
hierarchical SnO2/ZnO
25. SnO2 /rGO nanocomposite / Al2O3 spin coating Quantum wire 50 33 a 2 292 0.043 [96]
substrate
26. WO3 /rGO hybrid hydrothermal method nanocubes /nanosheets 0.5 32.7 a ~340 ~180 0.5 [97]
27. CNTs/SnO2/CuO Sol-gel Core (CNT) –shell (SnO2/ 40 19% 240 600 [98]
CuO) structure

oxide conduction band. Different structures of ZnO such as tetrapods
and bundle of nanorods have been used for fabricating toxic gas sensors,
though not all of them operate at room temperature. Ordered vertically
aligned ZnO nanorods decorated by flower like structures (Fig. 3a,b,c)
having large number of oxygen vacancy were prepared using carbo­
thermal reduction vapour phase transport by Hosseini et al, for H2S gas
sensing at room temperature [76]. It showed orders of increase in cur­
rent with 1 ppm H2S indicating good sensitivity though response and
recovery were relatively slower (Fig. 3d). Stable response after 5 months
storage in air for these sensors indicated stable morphology. Zhang et al.
fabricated a H2S gas sensor based on dendritic ZnO nanorods which
operates at room temperature [77]. Stability of these sensors is an issue
which needs further investigations. Thick film sensors based on ZnO
nanorods prepared by hydrothermal method were reported by Wang
et al. which showed good linear response to 0.05 to 1.7 ppm H2S at room
temperature [78]. Better sensitivity was observed for films produced by
hydrothermal method without surfactant templating. Room tempera­
ture H2S gas sensors based on the random network of ZnO nanowires
grown via hydrothermal method showed better sensing by modifying
the sensing layer with Au [87]. While comparing with pure ZnO nano­
wires and Au modified ZnO nanowires, the later showed a remarkable
16-fold increase in the sensor response over pure ZnO NWs toward 5ppm
H2S at room temperature.
Colloidal quantum dots (QDs) are low-dimensional semiconductor
nanostructured materials which have important potential applications
in gas sensor, due to the low-cost, solution processability, extremely
small size (a few nanometers in diameter) and high activity surface. In
the case of ZnO QDs, H2S sensing response was enhanced due to its large
surface-to-volume ratio which provides more active adsorption sites for
gas molecules on the surface [74]. Upon exposure to H2S, with great
difference in the adsorption energy between H2S and O2 on the surface
of ZnO QDs, oxygen adsorbates may be replaced by H2S followed by
donation of electrons to the ZnO conduction band decreasing its resis­
tance. ZnO nanorods prepared by vapor phase transport, Cu2O/Co3O4
(p-p) heteroarrays of nanorods and SnO2/CuO (n-p) heterojunctions
showed considerable response towards 1 ppm H2S [76,90,91]. However,
ZnO nanorods and Cu2O/Co3O4 heteroarrays had very slow response
and recovery times towards H2S while SnO2/ CuO heterostucture with
thick films had recovery only after heating. These results highlight the
advantages of heterojunctions for higher sensitivity, however, the
increased response and recovery times after gas exposure requires
further modifications of the structure in terms of film thickness etc for
easier gas diffusion, reaction and release of by- products. When ZnO
nanorod with flower like morphology was sensitized with Au, additional
active sites were introduced and affinity of Au toward H2S resulted in
higher sensor response and faster recovery to H2S. Au islands enhance
sensor response at room temperature by forming Schottky barriers at
Au–ZnO interface, introducing surface active sites, and increasing
effective surface area through surface coarsening [80]. Biomorphic
tube-like CuO (p-type) using pomelo white flesh as biotemplate showed
selective response to H2S with lower detection limit of 2-ppb and faster
response and recovery. This outstanding sensing performance resulted

8
C.A. Betty et al.
Fig. 3. FESEM micrograph (a top view, b magnified top view, c cross section) and d sensing performance of the vertically aligned ZnO nanorods towards H2S gas,
copy right [76].
from its unique structure and the transformation of semiconducting
p-type CuO to metallic CuS [82]. Au can also act as a catalyst for the
dissociation of molecular oxygen species attributing to the alteration of
barrier properties by the adsorption or desorption of adsorbed species
and/or H2S gas molecules. During recovery on exposure to dry air, CuS
was transformed back into CuO (CuS + O2 → CuO + SO2).
Indium oxide is an n-type semiconducting oxide having band gap of
3.6 eV. In2O3 with different shapes like whiskers, nanowires and
bipyramidal prepared by a simple carbothermal method is reported by
Kaur et al. [83]. It was evaluated that the whiskers can detect 200 ppb of
H2S, while bipyramids may be used for detection of the gas in a 10–80
ppm range at room temperature. The higher response of whiskers than
bipyramids could be attributed to a larger number of defects in the
whiskers as well as the reduced bandgap while the lower response of the
thick film made of bipyramids may be due to the reduced connectivity
between them [80]. In2O3 toruloid nanotubes (TNTs) show higher
response values, shorter response time and excellent selectivity
compared with In2O3 nanofibers. This was attributed to its special
sensing mechanism (sulfuration and desulfuration reaction) at room
temperature. As TNTs provide a hollow structure and a loose tube wall,
it provides better H2S gas diffusion. As more oxygen species are adsor­
bed on the surface of In2O3 more conversion to In2S3 takes place [84].
Porous In2O3 nanotubes (NTs) and nanowires (NWs) in cubic phase were
reported via electrospinning method using PVP as the polymer [85].
Both NTs/NWs sensors demonstrate excellent selectivity and sensitivity
for 1–100 ppm H2S. For In2O3 the proposed gas sensing mechanism is
that at relatively low temperature range (25–160◦ C) the sulfuration of
In2O3 is the dominant mechanism, and at relatively high temperature
range (160–300◦ C) the surface adsorption and the sulfuration both
contribute to the sensing response. At room temperature, In2O3 might be
undergoing partial sulfuration when exposed to H2S and highly resistive
In2O3 (79.8 and 80.9 kΩ for In2O3 NTs and NWs, respectively) gets
transformed into well-conducting In2S3. The reaction rates are affected
by many other factors, including grain surface reaction rate, intrapellet
diffusion reaction rate and the porous nature of In2O3 NTs/NWs sensors
[85].
CuO thin films prepared by oxidation of thermally evaporated Cu
9
Surfaces and Interfaces 36 (2023) 102560
films (thickness: 200 nm) on alumina substrate reported for sensing of
sub-ppm (100–400 ppb) H2S with fast recovery time. Sensing mecha­
nism is governed by oxidation of H2S by surface adsorbed oxygen (Fig. 4
(a)). For intermediate concentrations (500 ppb to 50 ppm), the response
curve is governed by both H2S oxidation and CuS formation (Fig. 4(b)).
However, for high H2S concentrations (> 50 ppm), surface of CuO grains
is found to convert into CuS, resulting in an irreversible response (Fig. 4
(c)) [88]. WO3 nanocubes/ rGO nanosheet hybrids shows ultra­
sensitivity to ppb level H2S gas at RT which is attributed to the large
specific surface area of the WO3 nanocubes, the formation of WO3/ rGO
heterojunctions enhancing electron transfer efficiency [97].
3.3. Nanostructured materials for room temperature operating H2 sensor
Hydrogen (H2) is a promising energy source for the future power
generation as it is renewable and abundant gas. It’s a clean energy
source as during combustion no emission of harmful gases takes pale.
The challenge in hydrogen usage is its safety; in case of leakage it can be
very dangerous and sometimes may cause explosion. Hydrogen being
colorless and odourless, it is not possible to detect by human organs.
Hence there is an utmost need for room temperature H2 gas sensor with
high sensitivity having fast response and recovery time. Table 3 lists the
materials studied for sensing of H2 [21,99-109].
PdO nanostructure gives high surface to volume ratio making it
possible to detect H2 gas as low as 30 ppm [21] in a wide linear range
from 30 to 4000 ppm with recovery happening either on exposure to
ambient light or by carrier gas flow. PdO thin film with well ordered,
nanocrystalline grains of size 20− 30 nm (Fig. 5 (a)) was deposited by
using LB technique. Repeated response of PdO film with 2000 ppm of H2
in the closed gas testing chamber is shown in Fig. 5b where the sensor
recovery was observed with opening the lid to the ambient light. PdO is
a p-type metal oxide semiconductor (< 2 eV) with near surface holes due
to the ionized adsorbed oxygen and OH species. The predominant sur­
face adsorbed O2− species is removed by H2 gas interaction forming OH
species, donating electrons to the conduction band of PdO which de­
creases the conductivity of the p type PdO film (O2− + H2 ↔ 2OH + e).
At room temperature, as desorption of the hydroxyl surface complex is
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

Fig. 4. Schematics and band diagrams showing different stages before and after the p-type CuO films were exposed to H2S gas of different concentrations, copy
right [88].

Table 3
Room temperature operated H2 sensor [a = Ra/Rg; b = ΔR/Rg: b1 = (Ra-Rg)/ Ra; c = ΔR/Rg x100%, d ¼ ΔR /Ra x100%; e ¼ Ra/Rg x 100%; f ¼ (Ig-Ia/Ia) x 100].
Sr. Nanomaterials studied for H2 Synthetic method Morphology Sensitivity details LOD Ref. No.
No. sensors ppm
Conc. Response tres(s) trec (s)
ppm

1. Nanostructured PdO thin film Langmuir-Blodgett nanoparticles 2000 15d <600 <60, shine 30 [21]
technique light
2. ZnO atomic layer deposition nanorod arrays 500 162 a 30 - 5 [99]
3. ZnO chemical deposition nanorod arrays 1000 500 f 176 116 [100]
4. ZnO /graphene Hydrothermal followed by nanotubes 10 14.3 30 38 10 [101]
CVD 100 28.1 e
5. Pd/SnO2 electrospinning nanofibers 1000 12.09 a 4 3 0.02 [102]
6. ZnO CVD nanowires 121 8d 29 - - [103]
7. ZnO aqueous chemical process nanotubes 500 29.6 d - - 5 [104]
5 11.9
8. ZnO thin films spray pyrolysis columnar 150 63 a 320 200 [105]
structure
9. MoO3 hydrothermal nanoribbons 1000 90 b1 14.1 - 0.5 [106]
10. Co/TiO2 self-assembly mesoporous 1000 4082 a 66 - 50 [107]
11. rGO/SnO2/PVDF hot press method wrinkled 100 49.2 34 142 10 [108]
structure 1000 71.4 d 52 242
12. SnO2/Pd hydrothermal nanosheets 400 ~540% 547 164 [109]

not feasible from the PdO surface, spontaneous recovery is not observed.
With an optical band gap of < 2 eV, PdO is photosensitive and under
light exposure, photogenerated electrons and holes produced in PdO
thin film contribute for recovery process. The surface hydroxyl interacts
with electrons forming negatively charged OH− species, while the holes
increase the conductivity (e- + h+ + OH ↔ OH− + h+). When the sensor
is again exposed with H2, the surface-adsorbed OH− species interacts
with hydrogen giving back the electrons to the PdO conduction band
(2OH− + H2 ↔ 2H2O + 2e). Thus, the conductivity is decreased for
p-type PdO thin film and this process is repeated. Similarly when
ambient air is used as carrier gas, the surface-adsorbed OH species is
replaced by the highly electronegative oxygen present in the air and the
film conductivity increases as the surface adsorbed oxygen further at­
tracts electrons from the Pd metal.
To compare the effect of preparation method, particle size,
morphology of ZnO on H2 gas sensing, few reports are included in
Table 3 [99,100,103-105]. A hydrogen sensor was prepared by Lim et al.
with Pd nanotubes using piezoelectric ZnO nanowires as templates [99].
However, the polycrystalline nature of palladium nanostructures made
the sensor much more sensitive to bending stress and its flexible design
caused changes in the electrical resistance due to formation of cracks
between the Pd grains. ZnO nanorod arrays based hydrogen sensor at
room temperature shows high sensitivity due to the high surface area to
volume ratio and the networks connections of vertically and oblique
nanorod arrays in the absence of seed layer [100]. ZnO nanorod array
was fabricated on an Nb/Si substrate electrode using anodic aluminium
oxides (AAO) as a nanotemplate and an atomic layer deposition method.
Surface area of the nanorod arrays can be controlled by adjusting the

10
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

Fig. 5. a FESEM image of PdO nanoparticles deposited on silicon substrate by LB method. (b) Response of sensor based on nanocrystalline PdO towards repeated
injections of 2000 ppm H2 gas. Down arrows indicate gas injection and up arows indicate opening of the sensor lid to ambient light, * lid closing of the test chamber,
copy right [21].

pore diameter or depth and the pore-to-pore distance in the nano­
template by adjusting anodization conditions. Single ZnO nanowires
based H2 sensors are an alternative for detecting low concentrations of
H2 due to their limited conduction channel that allows even a low
concentration of injected electrons to produce a measurable change in
their resistance [103]. Exploiting the peculiarities of a nanowire of
single crystalline ZnO with no grain boundaries, H2 gas detection at
room temperature has been reported [109]. However, manipulation and
creation of electric contacts with individual nanowire is a complex and
tedious process. ZnO nanotubes shows higher hydrogen response than
the pristine ZnO nanorods due to the larger surface area (i.e. through
assuming a hollow nanostructure) for adsorbing additional gas ions,
along with more oxygen vacancies to effectively sense gas ions [104].
Though many studies have been carried out on various types of nano­
wire sensors, the realization of a commercial sensor is still challenging
and selectivity, stability, reliability studies are still lacking. ZnO thin
film-based sensor showed significant sensitivity to hydrogen for con­
centration as low as 150 ppm at room temperature which was attributed
to the large roughness of the film [105].
ZnO nanotubes/graphene (ZNTs/G) self-assembled hierarchical
nanostructure showed outstanding enhancement in sensing properties
due to the formation of strong metalized region in the ZNTs/G interface
due to the inner/outer surfaces of ZNTs, establishing a multiple deple­
tion layer [101]. Mesporous Co/TiO2 prepared by self assembly method
showed significant response for H2. Li et al described about the sensing
mechanism in detail for H2 at room temperature with the potential
barrier formed due to oxygen species adsorption on Co-doped TiO2
mesoporous structures [107]. Manyfold increase in sensitivity was due
to the mesoporous structure of TiO2 giving rise to large number of active
sites both on the outer mesoposorus structure and inside the pores along
with Co- doping induced defect stuctures which increases the number of
active sites for gas adsorption. They observed better sensitivity at 250◦ C,
however, a decreased sensitivity with humidity was observed, since the
OH‾ species formed from the reaction between preadsorbed oxygen
species and water molecules decreases the potential barrier between the
Co-doped TiO2 grains. This study emphasises the role of doping in
increasing the gas sensitivity.
3.4. Nanostructured materials for room temperature operating SO2 sensor
Supfur Dioxide (SO2) is released when burning fossil fuel like coal,
automobile fules, fire crackers and from chemical incinerators. TLV for
SO2 gas is 2 ppm with typical symptoms such as sore throat, cough,
running nose and burning eyes for 5-50 ppm for 5 min exposure.
Inhaling > 50 pmm can cause swollen lungs and difficulty in breathing.
Table 4 lists the materials used for sensing of SO2 [35,34,110-114].
With SO2 gas exposure n-type metal oxides show increase in con­
ductivity with reaction products SO3 and release of electrons. Among the
very few reports for SO2 detection at room temperature PANI/WO3
heterostructure prepared by in situ one pot chemical oxidative method
and SnO2 prepared by LB method showed high sensitivity for SO2 [111,
34]. Though SnO2/PANI heterostructure offers better sensitivity for SO2,
its response and recovery times are very high compared to pure nano­
crystalline SnO2. Response comparison of undoped and Ni (2%) doped
SnO2 nanoparticles synthesized by low temperature polyol route showed
high sensitivity for SO2 at room temperature for the latter. The same
sensor showed high sensitivity and selectivity to NO2 with decrease in
current and stable response for 30 days [114]. Here we discuss in detail

Table 4
Room temperature operated SO2 sensor [a = Ra/Rg, d = (Ra-Rg /Ra) x100%].
Sr. Nanomaterials studied for Synthetic method Morphology Sensitivity details LOD Ref. No.
No SO2 sensors Conc. Response tres(s) trec ppm
ppm (s)

1. SnO2/PANI SnO2 LB method, PANI SnO2 nanoparticles/PANI 2 300 d 1000 2000 0.25 [35]
electrochemical heterostructure
2. Nanocrystalline SnO2 LB method nanoparticles 1 100 d 50 600 0.25 [34]
3. Pt–TiO2 /MoS2 LbL self-assembly nanosphere / nanosheets 1 5.2 d 35 63 0.25 [110]
4. PANI/WO3 in situ one pot chemical honeycomb type 10 10.6 d 180 180 5 [111]
oxidative method
5. Ag/PANI/SnO2, UV assisted nanostructure 50 20.1 a 100 100 [112]
sensing
6. MoS2 modified multi-wall chemical route nanocomposite 0.5–3 0.22-1.8 d 97.12 93.91 [113]
carbon nanotubes
7. Ni doped (2%) SnO2 polyol route Nano grain 10 6a 3 [114]

11
C.A. Betty et al.
response of the sensors based on SnO2 prepared by LB method, which
showed high selectivity towards SO2 among other gases, with stable
response for a period of 1 year.
Fig. 6a shows slightly porous, layered microstructure of the SnO2
thin film with uniform crystallites prepared by LB method [115].
Chemiresistive sensors are generally fabricated by depositing in plane
metallic contacts on the sensing film (Au, Ag, Pt, Al etc.) with matching
work function as the material, for connecting with the electro­
meter/multimeter for meaurements. After depositing gold interdigitated
electrodes on SnO2 thin film as shown in the photograph (Fig. 6b),
electrical characterization of this sensor was carried out by keeping in a
closed glass chamber with input and output ports for gas injection and
gas release respectively [116]. Among the many gases used for sensing
study such as; H2S, SO2, NH3, NO2, H2, CH4, CO, NO, O2, and CO2, the
sensor showed change in resistance only to H2S, SO2 (ΔR/R =400 for 1.5
ppm), NH3 and NO2. For H2S gas the response of the sensor in flow
conditions has been compared with draeger tube and the response was
comparable. Fig. 6c showed that for nanocrystalline SnO2, the sensing
towards NO2 occurs at room temperature with very high sensitivity of
two orders of change in current for about 1 ppm (ΔR/R =99) which
further confirmed the versatility of nanocrystalline SnO2 thin film. We
observed decrease in current as shown in Fig. 6c for NH3 which is a
reducing gas whereas other two reducing gases H2S and SO2 showed
increase in current making it selective among these reducing gases. This
is clearly a positive deviation from the known fact about macrocrystal­
line SnO2, that they are nonselective among reducing gases.
Among the various gas interactions studied, absence of any response
towards non-polar H2, O2, CH4, CO and NO for the nanostructured SnO2
thin film sensor indicated strong electro negativity of the surface. As
NH3 is a mild reducing gas, the interaction of NH3 with the surface
adsorbed O2 species is weak. However, partially positive H atoms of
polar NH3 molecule are attracted to negatively charged oxygen species
as shown in the schematic, Fig. 6(d). Studies using impedance methods
and related literature suggested that more stable NH3 molecules gets
weakly hydrogen bonded to the surface oxygen forming a metastable
species without significant charge transfer while acting as charge scat­
tering centres. This effect decreases the mobility of the charge carriers
and overall conductance [9]. The selectivity for NH3 among other
reducing gases for the nanocrystalline SnO2 thin film with crystallite size
of about 20 nm which was < 2LD, highlights the importance of crystal
Fig. 6. a Layered structure of the nanocrystalline SnO2 film prepared by LB method with the inset showing higher magnification of the micrograph, copy right [115].
b Photograph of the SnO2 thin film on quartz substrate with gold interdigitated electrodes with fingers each of 5 mm length and 100 µm separation between the
fingers. c Response of SnO2 sensor towards injections of various reducing and oxidizing gases [116]. d Schematic representation of the charge carrier distributions of
SnO2 thin film in the bulk, surface and with NH3 gas interaction, copyright [32].
12
Surfaces and Interfaces 36 (2023) 102560
size, negligible grain barrier potentials, charge on the surface adsorbed
species and charge carrier scattering effects in sensing [34,116]. This
study also affirmed the effects of nanocrystal size, large number of
surface adsorbed species on the nanocrystals etc., on the higher sensi­
tivity at room temperature towards selective gases for these sensors.
3.5. Nanostructred materials for room temperature operating NO2 sensor
Among the various toxic gases which needs to be monitored
constantly for health and safety reasons, NO2 is a common air pollutant
generated due to combustion of fossil fuels and its detection is required
in <1 ppm range (TLV is 3 ppm for 8 hours). Exposure beyond 3 ppm for
15 min causes increased inflammation in the lungs, reduced lung func­
tion and frequent asthma attacks warranting constant monitoring in air.
Table 5 lists the materials studied for NO2 [34,35,117-128] gas sensing.
TiO2 nanoparticles prepared by hydrothermal method has shown
high sensitivity with fast response and recovery times towards NO2
[117]. TiO2 surface on exposure to NO2 which is a highly oxidizing gas,
get adsorbed in the form of NO−2 (ads) and NO− (ads) with the
pre-adsorbed oxygen ions (O, O2− , O−2 ). This results in an increase of
grain surface depletion layer width and hence the sensor resistance
increase.
NO2(gas) + e− → NO−(ads) + O(ads);
NO2(gas) + O−(ads)
2 + 2e− → NO−(ads)
2 + 2O−(ads) [117]
SnO2 nanocrystalline tubes prepared by electrospinning showed
outstanding performance in sub ppb NO2 gas sensing (9.7 ppb) due to
following reasons; (i) one-dimensional hollow nanostructures with
adsorbed layers on both the outer and inner surfaces, overlapping and
connecting nanocrystallites with four or more adjacent grains through
necks (ii) a large number of active sites (chemisorbed oxygen: O− , O2− ,
O2−
2 ) and (iii) preferential orientation of the (101) crystal face [119].
Amorphous granular SnO2 thin films prepared by pulsed laser deposition
(PLD) displayed very high sensitivity of about 8000 (Iair/Igas) for 4 ppm
at room temperature with strong bias dependences on sensitivity [124].
PLD deposited SnO2 thin films consisted of 15 nm grains that were
separated by a network of thin cracks implying three-dimensional
growth of the film, significantly increasing the effective surface area.
ZnO/ZnS core-shell nanorods prepared by hydrothermal method with
C.A. Betty et al. Surfaces and Interfaces 36 (2023) 102560

Table 5
Room temperature operated NO2 sensor [a = Rg/Ra; b = ΔR/Rg: b1 = Ra-Rg/ Ra; c = ΔR/Rg x100%, d = ΔR /Ra x100%; e = Ra/Rg x 100%; f = Ig-Ia/Ia].
Sr. Nanomaterials studied for Synthetic method Morphology Sensitivity details LOD Ref. No.
No sensors for NO2 ppm
Conc. Response tres trec
ppm (s) (s)

1. SnO2/PANI SnO2 by LB method, PANI by SnO2 nanoparticles 1 23 d 25 400 0.02 [34]

electrochemical
2. Silicon/ZnO ZnO by chemical method ZnO nanoparticles drop 0.3 188 d 20 200 0.15 [35]
cast on porous silicon
3. Ni doped (2%) SnO2 polyol route Nano grain 1 850 a [114]
4. TiO2 hydrothermal nanoparticles 40 1093 a 48 52 0.02 [117]
5. SnO2 chemical precipitation nanocrystals with spherical 11 33 b1 100 250 ~3 [118]
shape
6. SnO2 electrospinning nanotubes 0.0097 16.1 b1 20 63 0.0097 [119]
7. ZnO nanoseed and surfactant nanowires 1 708 d 31 144 1 [120]
coassisted hydrothermal
8. ZnO physical vapor deposition nanowires 20 32 a 72 69 5 [121]
9. ZnO nanoseed-assisted nanorods 1 100 d ~300 1200 ~1 [122]
10. CuO sonochemical nanoplatelets 20 25.5 b1 34 - 5 [123]
11. SnO2 thin films pulsed laser deposition Amorphous and granular 4 7730 a 3 176 4 [124]
12. SnOX thin film RF sputtering thin film, grannular 10 19.4 b - - 1 [125]
13. NiO film chemical deposition & annealing Nanosheets porous. 0.14 100 d 75 174 0.02 [126]
14. Alumina decorated TiO2 vacuum pressure induction nanotubes with ordered 0.97-97 22-88 b1 16 8 0.97 [127]
technology and thermal mesoporous walls.
decomposition
15. ZnO/ZnS Core-Shell hydrothermal nanorods 0.1 1800 d - - 0.1 [128]
2.4 3000 d
16. CuO sheet /rGO nanohybrids one-pot solution process 1 14 f 66 34 0.06 [129]
17. 5% Cd-doped porous Co3O4 Simple in-situ microwave flat 2D nanosheets 10 3.38 a - 620 0.154 [130]
solvothermal reaction structures with lots of folds.
18. Graphene adhering to the hydrothermal sheets revealed a crumpled, 5 26.8 b 1.5 40 0.05 [131]
surface of porous Co3O4 slices rippled morphology.
19. ZnO nanorod/rGO additive-free solution synthesis, Ultrathin nanorods/ 1 119 d 75 132 0.05 [132]
seeding & oriented growth. nanosheets.
20. rGO / CeO2 bilayer facile spray & thermal reduction nanosheets / nanoparticles. 10 20.5 d 92 - 1 [133]
process
21. In2O3 microflowers/MoS2 2D Hydrothermal method and porous nanosheets- 5 344 a 37 0.00221 [134]
sheets mechanical mixing assembled 3D In2O3
microflowers
22. C-decorated TeO2, thermal evaporation nanowires 10 1.918 a [135]
23. CuO nanoflakes/ rGO hydrothermal with thermal nanoflakes/ nanosheets 5 400.8 d 6.8 0.05 [136]
nanosheets treatment 0.05 20.6 d

24. ZnO/SnO2 nanowires thermal evaporation followed by 1 28 a [137]

Au layer sputter deposition
25. In2O3 (NWs) electrospinning method and nanowires 5 740 a 0.01 [138]
sintering

an effectively lower band gap of 2.85 eV for the heterostructure showed
response of 1800 per cent for 100 ppb of NO2 highlighting the effects of
heterostructures with defect free interface resulting in very high sensi­
tivity [128]. Another heterostructure of porous silicon/ZnO (p-n junc­
tion) showed high response towards NO2 with fast response and
recovery and stable response. This sensor heterostructure, mechanism
for higher sensitivity and selectivity are discussed in detail in section 3.
7. b [40]. Nanoporous NiO film having network of nanosheets formed by
bunches of NiO nanoparticles (30-50 nm in size) with high surface to
volume ratio has reported a lower detection limit of 20 ppb with high
selectivity [126]. NiO films were prepared by low coast chemical bath
deposition and annealing method. Sensor response was stable for a
month, however, response decreased with increase in relative humidity.
The edge-enriched MoS2 nanosheets modified porous
nanosheets-assembled 3D In2O3 microflowers have been synthesized by
simple hydrothermal method and mechanical mixing method. These
sensors exhibited response as high as 343.09 for 5 ppm NO2, which is
309 and 72.5 times higher than the sensors based on the pristine MoS2
and In2O3 with excellent repeatability and long-term stability [134].
In2O3 nanowires prepared by simple electrospinning method showed
high sensitivity and selectivity towards NO2 suggesting the nanowire
geometry enhancing the surface reactions and hence the sensitivity
[138].
In order to detect explosive material, sensing of NO2 and NH3 in ppb
and ppt level is required. Explosives have very low vapour pressure,
hence their presence in sub ppm levels need to be detected. Recently
metallic nanowires and Mxene composites have shown high sensitivity
(ppt to ppb range) towards trace gas sensing such as NO2 and NH3 with
long term stability and resistance to humidity. Zhen et al [139] report
humidity (10 to 90% RH) resistant NO2 sensors operating at room
temperature using Ag2Te nanowires for ppb level detection (10%
response for 100 ppb) which showed stable response for 35 days. Au
loaded Te nanobelt sensor (Au@Te) prepared by one-pot hydrothermal
method was able to detect ~83 ppt nitrogen dioxide [140]. The
long-term stability of Au@Te sensor was evaluated for 28 days and the
sensor maintained stable sensing performance. However, with high
humidity levels the sensor response showed decrease. 2D niobium car­
bide MXene (Nb2CTx) nanosheets-supported polyaniline (PANI) nano­
composite (PANI/Nb2CTx) with enriched 3D spatial structure showed
ultrasensitive NH3 detection under humidity atmosphere [141].
As-developed PANI/Nb2CTx sensor exhibited high selectivity, sensi­
tivity, LOD 20 ppb and good long-term reliability toward 0.1− 10 ppm
NH3 with stable response up to 87.1 % RH. Authors suggested that due to
numerous hydrogen bonds between PANI and Nb2CTx, humidity effects
on the sensing properties of PANI/ Nb2CTx sensor was effectively
reduced. Double transition-metal titanium molybdenum carbide
(Mo2TiC2Tx) for NO2 gas molecule showed detection limit of 2.5 ppb at
room temperature. Authors demonstrated a portable, wireless NO2

13
C.A. Betty et al.
monitoring system for gas leakage searching and dangerous warning
based on Mo2TiC2Tx/MoS2 gas sensor [142].
3.6. Nanostructured sensors for volatile organic compounds and other
gases at room temperature
Wang et al. [143] report flower-like ZnO nanostructures assembled
by porous nanosheets on GaN using electrodeposition which forms a
(ZnO/GaN) heterojunction and it was found to sense ethanol gas at room
temperature with a detection limit of 100 ppb and excellent selectivity.
The authors suggested that due to the interspaces between the connected
nanosheets and inner pores of nanosheet, diffusion and adsorption of the
target gas can be accelerated on the surface of ZnO improving the gas
sensing properties. Room temperature CO gas sensor based on Ag-Z­
nO/MoS2 ternary composite fabricated by layer-by-layer self-assembly
route showed a detection range in ppm [144]. Seekaew et al. [145]
reported room temperature toluene gas sensor based on TiO2 nano­
particles decorated 3D graphene-carbon nanotube nanostructures (3D
TiO2/G-CNT) which exhibited substantially higher toluene response,
sensitivity and selectivity than 3D G-CNT, TiO2-CNT, graphene and
CNTs over a low concentration range of 50–500 ppm. ZnO/rGO micro
Schotky junctions have been reported to sense nitroexplosive vapors in
the ppb range [146].
3.7. Exploring the specific advantages and intriguing effects of
heterostructures in room temperature toxic gas sensing
Jian et al discuss in detail about the advantages and feasibility of
using composite functional materials and heterojunctions as chemir­
esistive sensors for better gas sensing performance such as better gas
selectivity, sensor stability, cost effectiveness and higher sensitivity
Fig. 7. a FESEM micrograph of PANI deposited SnO2 film with inset showing the nanocrystalline SnO2. b Schematic of the sensor structures #1 &2 with gold strip
contacts numbered from 1-4. Sensor #1 consists of 1 & 2 strips while sensor #2 consists of strips 3 &4. c Response of sensor #1 towards various gases. d Schematic of
energy levels with appropriate band bending at the PANI-SnO2 interface. e Response of sensor #2 towards various gases, copyright [35].
14
Surfaces and Interfaces 36 (2023) 102560
compared to sensors based on pure materials [147]. By combining the
piezotronic effect [148,149] with the Schottky contact, ZnO micro/­
nanosensors were reported for the detection of hydrogen and nitrogen
dioxide at room temperature. Heterojunctions formed by core shell
nanowires of two different metal oxides with one diameter (inner or
outer) of the order of LD improves the selctivity and sensitivity. Using
heterojunctions or composite materials there is possibility for sup­
pressing the responses to other specific gases making the sensor more
selective for one gas. Therefore a detailed analysis of the heterojunction
influence such as interfacial space charge layer effects, type of hetero­
junction etc. may provide an understanding for designing a composite
material or a heterostructure for a given sensing application [150].
Wang et al. [151] presents a review of organic-inorganic structures for
gas sensors capable of enhancing the gas sensing performance. We
discuss here few types of heterojunctions which helped in improving the
sensor performance.
3.7. a. Effects of the type of heterojucntion and interfacial film thickness on
sensing characteristics
Here we consider two types of heterojunctions which has resulted in
better selectivity and higher sensitivity. SEM micrograph of SnO2/PANI
heterostructure with the inset showing the nanostructured SnO2 thin
film is shown in Fig. 7 (a). PANI deposition on slightly porous and well
orded SnO2 film resulted in highly porous heterostructure which helped
in target gas molecule diffusion. Two types of heterojunctions consid­
ered are SnO2/PANI with: (i) sensor #1 by taking in-plane contacts with
one contact each on SnO2 and PANI (horizontal heterostructure with
gold strips contacts (1 &2)) and (ii) out of plane contacts on the vertical
heterostructure of PANI deposited on SnO2 (two gold strips 3&4) as
shown in Fig. 7(b). [35]. Both types of sensors #1 &2 showed very good
response towards NO2; sensor #1 with a response of increasing current
C.A. Betty et al.
and faster rcovery while sensor #2 with decreasing current and no re­
covery (Fig. 7(c) and 7(e)). Sensor #2 also showed 300% response to­
wards 2 ppm SO2 with slow increase in current (Fig.7e). SnO2/PANI
hetetrostrucutre form p-n junction whose junction space charge layer
can get modified by interaction with toxic gases leading to better
sensitivity and selectivity. SnO2 being n-type and PANI being p-type,
sensor #1 consist of an in-plane horizontal p-n type junction as shown in
Fig. 7d, which suppressed the SO2 response while the response of the
PANI becoming dominative for NO2 gas. However, in the case of sensor
#2, the p-n junction in the out of plane geometry became more domi­
nant with SnO2 properties which showed higher response towards SO2
as well as NO2 as observed for pure SnO2 thin film [35]. For this sensor,
the increase in response time for SO2 gas could be due to the combined
effect of the out of plane heterojunction and SnO2 grain boundaries
compromising the resposne characteristics.
Since it is preferred for heterostructure films, to have either or both
film thickness of the order of Debye length for optimum control of space
charge layers for maximum sensitivity, SnO2/PANI structures were
prepared with different PANI layer thickness. The PANI molecules can
readily react with protonating and deprotonating, or reductive and
oxidative agents, causing either a change in the electronic structure of
the polymer or by reducing the mobility of the carriers. So on interaction
with NO2, while there was removal of electrons from both SnO2 and
PANI, the former had decrease in current and in the latter current
increased with associated changes in SnO2/PANI interfacial space
charge layer and at the SnO2 grain boundaries, resulting in different
types of response in in-plane and out of plane structures. The hetero­
structure of SnO2/PANI with 15 layers showed maximum sensitivity
underlying the depletion layer effects at the interface as shown by the
respective band bending in Fig. 7d. In fact, this type of detailed studies
on heterostructure geometries and interfacial film thickness dependance
opens up innumerable possibilities for sensor characteristics
optimization.
15
Surfaces and Interfaces 36 (2023) 102560
3.7.b. Effects of interface morphologies of heterojucntion on sensing
characteristics
The effects of substrate morphologies on the gas sensing properties
were explored using ZnO nanoparticles deposited on bulk silicon wafer
(p-type) which forms Si/ZnO and another heterostructure consisting of
ZnO nanoparticles deposited inside the pores of p-type porous silicon
(PS/ZnO, with micro-pn junctions) (Fig.8a-d) [40]. Both sensors were
found to be displaying high sensitivity and selectivity to NO2 in the ppb
concentration range at room temperature with maximum sensitivity
being at 40◦ C. In the case of ZnO deposited on silicon substrate Si/ZnO,
there would be space charge layer formation due to polarization of
charges at various interfaces between p-type bulk Si surface and n-type
ZnO film, between ZnO/Au contacts and between the ZnO nanograins
resulting in three types of potential barriers. In the PS/ZnO structure,
there would be additional space charge layers at the interface between
each of the nanocrystalline silicon pore walls and nanocrystalline ZnO
[40]. SEM micrographs of PS/ZnO and Si/ZnO are shown in Fig. 8a.
Fig. 8b shows the sensor stucture schematic with Au strip electrodes.
Band alignments and the corresponding potental barriers of Si/ZnO and
PS/ZnO are shown in Fig. 8c and d. Upon interaction of target gas with
the surface adsorbed oxygen species, the charge carrier concentration in
the ZnO surface changed, modifying the potential barriers due to the
space charge layers at the various interfaces as discussed above, leading
to an overall change in the current. It was also observed that PS/ZnO is
highly selective to NO2 (Fig. 8e). The increase in sensitivity at 50◦ C for
Si/ZnO towards NO2 gas compared to 30◦ C is shown in Fig. 8e. This
sensor also showed some response, though minor, towards SO2 and NH3
indicating the dominant effects of ZnO on a planar Si/ZnO hetero­
structure, further emphasizing the importance of morphology and het­
erostructure compositions of the nanostructured materials for better
sensing proprties.
Fig. 8. a SEM micrograph of ZnO
nanoparticles filled porous silicon (top).
(below) SEM micrograph of ZnO nano­
particles on Si surface. b Schematic of
PS/ZnO with gold strip electrodes. c
Energy levels with appropriate band
bending at the interface of Si/ZnO.
d Schematic of the micro­
heterojunctions between Si and surface
charge depleted ZnO due to the ZnO
filled micropores of the Si. e Specific
response of PS/ZnO sensor towards
various concentrations of NO2 in ppb
while no response seen towards SO2 (1
ppm) and ethanol (20 ppm) at 25◦ C. f
Response of Si/ZnO sensor initially at
30◦ C and subsequently at 50◦ C towards
various concentrations of NO2 in ppb,
NH3 (10 ppm) and SO2 (2 ppm), copy­
right [40].
C.A. Betty et al.
4. Reliability, humidity effects and stability of the
nanostructured thin film based trace gas sensor
One of the apprehensions about the nanostructured materials for
device applications, especially in gas sensors was their stability and
repatability issues. Varying humidity conditions depending on the
climate can further pose problems for low temperature operating sensor.
This requires detailed understanding of the surface adsorbed ionic spe­
cies, gas sensing mechanism, sensor regeneration and effects of hu­
midity. Since SnO2 is generally considered as a stable metal oxide and
widely used as a prototype of metal oxide semiconductors for gas sensing
applications, here we discuss the detailed gas sensing study carried out
at room temperature on thin films of nanostructured SnO2 in terms of
their morphology, effects of surface states on the nanograins and the
humidity effects. S. Wicker et al. have studied the influence of humidity
(1-80% RH) on SnO2 surface for CO detection at high temperature using
Diffused Relectance Infrared Fourier Transform (DRIFT) Spectroscopy
and first principle calculations. It was concluded that water vapor in­
terferes with CO detection depending on the active surface and the
concentration of oxygen vacancies [152]. Water vapor can either act as a
reducing species or reoxidation route of the oxygen vacancies depending
on the active surface. G. Korotcenkov et al. reported that the adsorp­
tion/desorption of both water and oxygen controlled the kinetics of gas
response for the SnO2-based sensors [153,154]. Anosimov et al. have
studied the effect of humidity on SnO2 and suggested that water mole­
cules dissociate on the SnO2 surface producing hydroxyl species capable
of acting as electron donors while decreasing the densities of chem­
isorbed atomic oxygen and lattice oxygen atoms [155]. When H2O
molecules are adsorbed on the surface of sensing layer, they form OH− .
The preoccupied OH− adsorption hinders the chemisorption of oxygen
species and migration of target gas on the surface, which results in the
low sensing properties [156]. Nanostructured SnO2 prepared by LB
method has been studied for humidity effects at room temperature both
by DC resistance AC inpedance methods. No significant change in
resistance/impedance was observed till the humidity in the surround­
ings was about 98% confirming the superiority of the nano-grained thin
film SnO2 sensors compared to other thin film gas sensors [10,116,156,
157]. The reason could be the prevalence of dominant surface adsorbed
oxygen species on the nanostructured SnO2 which are responsible for the
sensor response than the OH radicals reported for macrocrystalline
SnO2. Equally, the adsorbed water vapour could be acting as the reox­
idation route of the oxygen vacancies on nanocrystalline SnO2 surface
with low surface activation energy as suggested by Wicker et al. [152].
Though the interaction of target gas with surface adsorbed oxygen
species is mainly responsible for sensor response, the diffusion of oxygen
species and/or hydroxyl ions across the grain boundary barriers at room
temperature are trivial due to the uniform crystallies, suppressing its
effects on potential barrier modifications and making room temperature
operating sensors more robust.
Rajnish et al. [158] reported the stability and reliability studies of
high temperature operating SnO2/Pt and SnO2-Cu/Pt based CO sensors
carried out for about 2 months with various thermal stresses. It was
observed that the film cracks during large number of operation cycles
during high temperature operation. The cracks effect the performance of
the device in terms of resistance and hence the reliability. It was
observed that the Cu doping suppresses the cracking due to thermal
cycles compared to pure SnO2 thin film. Doping changes the properties
of grain boundaries, inhibiting ionic diffusion between the grains,
resulting in better stability of devices when operated at higher temper­
atures. Sensor degradation due to composition change, cracks and ionic
migration due to thermal stress are negligible in the case of thin film
sensors operating at room temperature. However, degradation due to
poisoning effect is a possibility for the room temperature operating
sensors. Repeated measurements carried out at room temperature over a
period of one year on an unpackaged nanocrystalline SnO2 sensor that
was exposed to various gases in ambient conditions, showed the same
16
Surfaces and Interfaces 36 (2023) 102560
response to ammonia with slower response and recovery times indi­
cating the stability and reproducibility of the sensor [116]. The elec­
trical contact and lead materials of the sensing films also play an
important role in the stability of the sensors. For sensors which detect
corrosive gases, the contact material should be totally inert, such as Au
or platinum. For cost effectiveness, if silver paste is used for contact
making, the corrosive gases corrode the contacts, decreasing the sta­
bility and reliability of the sensor. Though the stability and reliability
studies are very important aspects for a sensor, not many reports are
available about the long term stability and reliability studies of the room
temperature operating nanostructured metal oxide thin films.
5. Role of surface adsorbed species on room temperature trace
gas sensors
Few reports have discussed gas sensing properties of metal oxide
semiconductors, enhanced oxygen diffusion in nanostructures and the
difference in carrier transport that may occur in macro and nano­
structured materials [159–162]. Some studies on the sensitivity and
sensing mechanism based on the temperature dependent changes in the
grain barrier potentials on interaction with reducing and oxidizing gases
have been carried out to understand the effects of surface adsorbed
species [2–10]. XPS studies on nanocrystalline SnO2 thin films had
suggested the presence of surface adsorbed oxygen species. Authors
carried out experiments on SnO2 sensor to understand the role of surface
adsorbed oxygen species in the room temperature sensing mechanism by
monitoring the sensor response under vacuum and in ambient condi­
tions [115]. Under vacuum, in the absence of surface adsorbed oxygen,
the sensor response decreased, response time and recovery time
increased for the same NH3 gas concentration compared to that in
presence of ambient air (Fig. 9). The study suggested that NH3 sensitivity
decreases in vacuum as compared to that in air due to reduction in
number of surface adsorbed oxygen species on SnO2 in vacuum. To
further confirm the role of surface adsorbed species in the conduction
processes at the nanocrystalline grain boundaries of SnO2 thin film and
at the film-electrode interface as a function of temperature, multifre­
quency impedance spectra were recorded in the temperature range of 26
to 125◦ C [115]. We used this very simple and easily available approach
of comparing the DC current and AC impedance repsonses of the sensor
film which makes it possible to separate the specific effects due to
electronic and ionic contributions for gas sensing. It is based on the
premise that specific electronic and ionic contributions from thin film
surface/electrode contacts, bulk of the film and grain boundaries be­
tween the grains of the thin film etc. correspond to different kinetic
Fig. 9. Response of the sensor towards NH3 gas under vacuum and in presence
of air. Upper arrows indicate the opening of the stop cocks after response
saturation, copyright [115].
C.A. Betty et al.
phenomena of the sensor response which can be delineated by imped­
ance studies during real time gas interaction [159]. The study concluded
that higher conductivity observed for the sensor at higher temperatures
is due to the combined effects of thermally assisted carrier generation
and increased diffusion rate of oxygen ionic species at the grain
boundaries, though the contribution due to the latter decreases with an
increase in temperature as the desorption of ionic species takes place
[115,116]. Using multifrequency impedance data the activation energy
required for charge transport between the grains of nanocrystalline
SnO2 thin films was estimated as < 30 meV, which enabled them to
operate at room temperature with fast response and recovery [116].
Further, gas specific transient impedances observed at single frequency
(77 Hz) during real time impedance measurements demonstrated spe­
cific detection of NH3, H2S and NO2 – each with specific transient
response, using single sensor at room temperature in presence of other
interfering gases [34,116]. This observation promises that such a mul­
tigas sensor can be realized by operating the sensor at room temperature
using low frequency ac signal without any complex electronics.
6. Concerns regarding reliability of sensor operating at room
temperature
Gas sensing based on either bulk materials or nanostructured mate­
rials encounters many challenges; cross sensitivity, weak selectivity and
durability. Moreover, for the low temperature operating sensors, the
drawbacks could be slow recovery and shorter life time due to accu­
mulation of the by-products of the gas interaction on the material sur­
face. So, their development and application are restricted because of
issues such as a slow response on aging, poor selectivity and regenera­
tion issues. High operation temperature leads to agglomeration of the
nanocrystals resulting in loss of sensitivity with time [163] whereas loss
of sensitivity issue does not affect low operation temperature sensors.
Most of these sensor properties can be regenerated by heating the
sensing films at 60◦ C for an hour. Periodic recalibration of the sensor
also can avoid reliability issues. Since chemiresistive gas sensors mostly
detect gases depending on their redox properties, they may experience
selectivity issues. Though one sensor material could be highly selective
to one of the reducing gases, the same gas sensor can be affected by
non-target gases which have similar chemical characteristics while
detecting a mixture of similar gases. This may lead to inaccurate display
of the target gas concentration which can be alleviated by pattern
recognition or by using appropriate electronics. Further the accuracy of
the gas sensor is directly related to temperature and humidity of the
working environment [164,165]. Since resistance of the semiconducting
material depends on the temperature, there could be variations in the
sensitivity with temperature depending on the climatic conditions,
especially for low temperature operating ones. This can be controlled by
hermatic sealing of the sensor housing, baseline resistance tracking
electronics and by providing constant temperature operation. In recent
years, there has been a significant improvement in sensor design along
with the advances in micro- and nano-fabrication technology and the
use of newly designed materials, leading to the development of
high-performance and reliable gas sensors [166].
7. Conclusions and future scope for room temperature operating
trace gas sensors
For chemiresistive sensors, the charge carrier density of the material
and surface potential barrier due to the space charge layer thickness
arising from charge depletion caused by surface adsorbed species play
very important roles in deciding the response of the sensors with target
gas interaction. Operating temperature of the sensor based on poly­
crystalline material is also decided by the surface potential barrier which
decides the activation energy required for charge transport among the
crystallites towards the electrodes. The size and shape of the nano­
structures also play roles in deciding the sensitivity of the material as the
17
Surfaces and Interfaces 36 (2023) 102560
surface area pertains to sensing signal strength and crystal size and
shape determines the extent of the surface depletion layers. Further, the
extent of surface depletion layers decides the partial or total insulating/
conducting property of the sensing materials. Structures such as nano­
wires, nanorods, nanoparticles etc. with one dimension of the order of
Debye length offers partial or complete depletion of charge carriers
resulting in switching of the electrical properties from semiconducting
to insulator leading to significant changes when interacting with even
small quantities of target gases. Recent studies discussed in this review
suggest scope for higher sensitivity, selectivity, long term reliability and
low temperature operation for trace gas sensors. These studies high­
lighted the effects of crystallite size, crystal morphologies, surface
adsorbed species, material preparation method and type of hetero­
structures or composite morphologies for improving the sensor perfor­
mance. Some of the points are listed below
i) Low dimensional nanostructures such as 1-D and 2-D show large
surface to volume ratio which increases the sensitivity.
ii) Low activation energies required for the charge transport across
the grain boundary potential barrier in 2-D materials, potential
barrier free charge transport in 1-D structures make the room
temperature operation realizable in these nanostructures.
iii) Large number of highly active surface states results in very high
number of fast surface reactions leading to higher sensitivity to­
wards the target gas and fast response-recovery times.
iv) Charge and chemical characteristics of surface states on these
nanostructures determine the target gas interactions, selectivity
and humidity effects of the sensor performance.
v) In addition to the large surface areas of the nanocrystals, quan­
tum size effects and high surface energy due to the surface states
also significantly enhance the performances of the sensor. Better
gas selectivity for the sensing material can also be achieved by
doping in nanocrystals. So depending on the morphology, di­
mensions and doping of the nanostructures, the activation energy
required for the charge carrier transport gets modified which
effect the temperature of operation and sensitivity.
vi) Gas selectivity and sensitivity of the sensors can be further
improved using heterostructures or composite structures which
switch from p-n junctions to Schottky junctions or vice versa with
target gas interactions. Composite materials and thin film heter­
ostructures of semiconducting nanostructures, which modify/
switch the heterostructure junction barrier properties (from
Schottky to p-n junction or vice versa) due to target gas interac­
tion, provide exclusivity/nullification of material responses to
certain gases resulting in higher selectivity.
vii) For thin film heterostructures, control of interfacial film thickness
and number of heterojunctions also is important whose optimi­
zation can be transformed into high selectivity and sensitivity.
There exists tremendous scope for designing new material compo­
sitions, nanostructure morphologies, nanostructure dimensions by cost
effective preparation methods, nanostructured film dimensions and
their thickness control for improved sensor performance with reliable,
room temperature operation. Need of the hour is more rigorous stability
and reliability studies of these room temperature operating sensors over
longer durations in the ambient conditions and in presence of gas mix­
tures to make them viable for commercial applications.
7.1. Choice of materials and technologies
For the sensors which are used for the short term use, nanocrystalline
material can be deposited in the form of thin films by cost effective
techniques such as drop casting, spin coating and dip coating. For long
term operation of the sensors, sensing material should be chemically
stable and they should not be affected by humidity variation. Further the
baseline drift and sensitivity variation of the sensing material should be
C.A. Betty et al.
minimum (±10%) within 10-50⁰C range. For fabricating chemiresistive
sensors the contact electrodes can be in the form of dots or strips or
interdigitated. Interdigitated electrodes are suitable for miniaturization
since they provide larger contact area with the sensing film in a small
volume. The contact and lead materials also play an important role in
the stability of the sensors. There should be work function matching
between the sensing material and the contact material. For sensors
which detect corrosive gases, the contact binding material should be
totally inert such as Au or platinum.
Chemiresistive gas detection system consists of a gas sensor enclosed
in a housing, and electronics for the conversion of sensing signal into
electrical (analog) signal and then to digital signal for readout. The
changes in the characteristics are recorded before and after exposure of
target gas. Electrical signal change such as output voltage or output
current/output impedance of the gas sensor can be used to get an idea
about gas concentrations. Feedback and appropriate corrections can be
used to provide the actual change in output regardless of baseline drift
and noise. For the electronic device, change in output voltage mea­
surement can be the best way for measuring the changes in output as
they are simple, usually linear functions of the measurement. Micro­
controllers along with analog to digital converters are required for
readouts. Advanced micro- and nano-fabrication technology enables
miniaturization of these sensors into micro-sized gas sensor arrays while
maintaining the sensing performance. Therefore, a combination of
advanced fabrication technologies for controlling the sensor design and
well studied nanomaterials or composites with novel morphologies
could be the future scope for room temperature operating, reliable
sensors.
7.2. Application areas
Increase in the number of industries, automobiles and construction
sites gives rise to polluting and toxic gases in our environment leading to
green-house effect, acid-rain, ozone depletion, global warming etc.
These are some of the serious environmental and human health issues
which world is facing right now. NO2 is the main cause for acid rain and
the main sources are automobile exhausts and industrial plant exhausts.
To monitor NO2 levels in exhausts, room temperature operating, mini­
aturized, portable chemiresistive sensors are appropriate. SO2 also
causes acid rain. To monitor the main source of SO2 such as coal mine
and natural gas manufacturing industries, these sensors can become
very useful. H2S is a by-product of manufacturing of many chemical
substances such as pesticides, pharmaceuticals and it is widely present in
landfills. High levels of H2S can cause explosion even with automobile
ignition, becoming a threat to human life. Therefore, pocket sized H2S
sensors are essential for monitoring in oil and petroleum industries,
mining sites and waste water treatment plants etc. NH3 sensors find
applications in fertilizer, chemical and refrigeration industry. H2 has
become a very popular clean-energy source with increasing demand.
Hydrogen is neither a toxic gas nor any explosives contain hydrogen gas,
still its detection has been included in trace gas sensing category because
of its explosive nature at concentration above 4%. Hydrogen has the
potential to cause global environmental impacts both on the strato­
spheric ozone layer and on climate change. Moreover, because of
tasteless, colourless and odourless nature of H2, it is difficult for human
sensing organs to detect its leakage in the surroundings, further stressing
the need for room temperature operating sensor alarms.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
18
Surfaces and Interfaces 36 (2023) 102560
Data Availability
No data was used for the research described in the article.
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