See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/270587471

Gas sensing mechanism of metal oxides: The role of ambient atmosphere,

type of semiconductor and gases -A review

Article · January 2015

CITATIONS READS

51 10,380

2 authors:

Prabakaran Shankar John Bosco Balaguru Rayappan

Sungkyunkwan University Natural Science Campus SASTRA University
48 PUBLICATIONS   612 CITATIONS    306 PUBLICATIONS   4,264 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Information security View project

Image Encryption View project

All content following this page was uploaded by Prabakaran Shankar on 19 September 2016.

The user has requested enhancement of the downloaded file.

Science Letters Journal Sci. Lett. J. 2015, 4: 126

Gas sensing mechanism of metal oxides: The role of ambient atmosphere, type of
semiconductor and gases - A review

Prabakaran Shankar, John Bosco Balaguru Rayappan*

School of Electrical & Electronics Engineering (SEEE) & Centre for Nanotechnology & Advanced Biomaterials (CeNTAB)
SASTRA University, Thanjavur – 613 401, India
*
Author for correspondence: John Bosco Balaguru Rayappan, email: rjbosco@ece.sastra.edu
Received 01 Aug 2014; Accepted 08 Oct 2014; Available Online 08 Oct 2014

Abstract

Metal oxide thin films have emerged as a promising choice in the gas sensor industry. Several key parameters such as physical and
chemical characteristics of the metal oxides, synthesis techniques used, nature of gases, type of atmosphere and the operating temperature
collectively influence the sensor properties. The chemiresistive property change in the conductivity associated with adsorption and
desorption of gas molecules on the metal oxide surface, is the principle of sensing mechanism. However, owing to the multitude of factors
involved, understanding the interaction mechanism behind the sensing property remains a challenge. In this review, the chemical kinetics of
reduction-oxidation (REDOX) reactions occurring at the metal oxide surface during its interaction with various gases in dry and wet
atmospheres have been analysed. Along with, the sensing characteristics of the metal oxide materials toward the detection of toxic gases, the
various determining factors of sensing behaviour of metal oxides and the role of gas molecules have been discussed. For this study, the most
toxic, combustible and hazardous gases such as CO, CO2, NO2, SO2, NH3, H2S and C2H5OH have been considered as target gases while,
ZnO, SnO2, In2O3, WO3 and CuO, NiO represent n-type and p-type semiconductors respectively to study the influence of base materials.

Keywords: Metal oxide gas sensor; REDOX reactions; Temperature; Nanostructures; Thin films

1. Introduction In the recent past, the development of nanoscience and

technology has strongly influenced this field and lead to a
The complex and tunable nature of electrical paradigm shift in the sensor technology [28–30].
properties of metal oxides makes them an interesting and
attractive material for various applications such as solar cells 1.1. Principle
[1,2], optoelectronics [3–5], spintronics [6], piezoelectric [7] The metal oxide gas sensor works on the principle of
and gas sensors [8]. In 1953, Brattain et al. and Bardeen et al. chemiresistance viz. the change in electrical conductivity or
[9–11] conducted a systematic study on the changes in the resistivity of thin films on exposure to a target gas. In other
electrical properties of semiconductor materials due to the words, gas molecules interacting with the metal oxides either
interaction of gas molecules at the surface. The detailed study act as a donor or acceptor of charge carriers (Receptor
of the interaction of gas molecules with semiconductor function), and alters the resistivity of the metal oxide
materials prompted the research on metal oxides for gas (Transduction function) and it is shown in Figure 1. The
sensing applications. In 1962, Seiyama et al. [12,13] and increase or decrease of resistance of the metal oxide thin film
Taguchi et al. [14] observed the changes in the electrical
behaviour of zinc oxide and tin oxide due to the changes in the
gas composition at the ambient atmosphere. Figaro Inc., a gas
sensor company based on metal oxides started by Taguchi in
1968 still stands as one of the world‟s leading gas sensor
manufacturer. Since 1968, the science and technology of metal
oxide based semiconductor gas sensors have been evolving
due to the significant contributions from researchers across the
globe. The sensitivity/response of the metal oxide gas sensors
towards a particular target gas can be improved by using metal
additives/doping [15–18], by reducing grain size [19,20], or by
altering operating temperature [15,16], and humidity [21].
Another important characteristic parameter namely selectivity
of the sensor with reference to the type of gas (oxidizing/
reducing) [22] and conductivity of the semiconducting
material [15], effect of dopants [23] and nature of the selected
oxide materials have also been studied. Simultaneously,
theoretical contributions from different researchers [24–27]
help to have a better understanding about the science of Figure 1. Schematic of metal oxide thin film gas sensor.
interaction between the metal oxide surface and gas molecules.
Cognizure 1
www.cognizure.com/pubs © Cognizure. All rights reserved.
 Science Letters Journal
Table 1. Mechanism of sensitization by metal or metal oxide additive (Reprinted with permission from Ref. [20] Yamazoe, Sens. Actuat. B
5 (1991) 7. © Elsevier Publishing).
Type Chemical
Model
Role of noble metal Activation and spill-over of sample gas
Origin of gas-sensitive
Change of adsorbed oxygen concentration
properties
Example Pt-SnO2
depends upon the type of majority carriers in the
semiconducting film and the nature of gas molecules (whether
oxidizing or reducing) in an ambient atmosphere. For n-type
materials, oxidizing gases (acceptor) increase the resistance of
thin film while, reducing gases (donor) decrease and are
correspondingly converse for p-type materials [31]. The
mechanism of receptor function (REDOX) together with the
transduction function describes the chemiresistive behaviour of
the metal oxide gas sensors. The metal oxide sensors can be in
the form of sintered pellets or thick and thin films. In specific,
the geometry of the crystallites of the grown crystals and their
interconnectivity between crystallites play a most responsible
role in determining the receptor and transduction functions.
This is one of the main reasons behind the influence of
nanotechnology in this field, which manipulates matter on an
atomic and molecular scale. Thus nano dimension plays a
major role in the development of gas sensors [32].
The chemiresistance property of the metal oxides can
be related to the width of the space charge region formed on
the crystallites due to the transfer of electrons during the
adsorption and desorption of gas molecules. The width of the
space charge region acts as a potential barrier in the
conduction process between the grains and induces changes in
the Fermi level. The process of creation and annihilation of
electrons form the conduction band results in band bending
and Fermi level modulation. When oxidizing gas interacted
with n-type material the band bends upward due to the
depletion of electrons and while, the band bends downward
due to the accumulation of electrons for reducing gas. Hence,
one can infer the direct relation between space charge region
and band bending which depends on the carrier concentrations
in the grain that, in turn, depends upon the size and shape of
the grain.
1.2. Influencing factors
In 1972, Seiyama et al. [33] reported that additives
can promote gas sensitivity and rate of response under certain
conditions by modifying its surface. In 1991, Yamazoe et al.
[20] have found an inverse correlation between the response
and its grain size. The grain size in the metal oxide thin films
can be controlled by modifying the synthesis parameters [34]
and adding suitable dopants with appropriate host materials
[20]. Reducing crystallite size might have influenced on the
width of space charge region which, aids the chemisorption of
gas molecules and sensing process. The mechanism of
2 Cognizure
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
Electronic
Electron donor or acceptor
Change of oxidation state of noble
metal
Ag2O-SnO2, PdO-SnO2
sensitization or response enhancement by additives are found
to be different in different metal oxide materials. Yamazoe
[20] have proposed two types of sensitization mechanisms;
chemical and electronic as shown in Table 1. In chemical
sensitization, the promoters residing on the metal oxide surface
facilitates the chemical reactions between target gas and metal
oxide surface through the spill- over phenomenon, for example
Pt, Pd–SnO2 [20]. On the other hand, in electronic
sensitization, the electrical property of the metal oxide is
changed through the change in redox state of the promoter, by
acceptor or donor charges from gas molecules, for example
Ag- SnO2 [20].
“Promoters are additives to metal oxides, which help
in improving their sensing characteristics by lowering the
energy required for chemisorption of gas molecules on the
semiconductor surface” [35]. “Adding a suitable dopant can
stabilize a particular valence state and increase the electron
exchange rate or stabilize the metal oxide against reduction”
[35, 36]. The choice of the synthesis method and the
composition of mixture of precursors used in the synthesis
strongly affect the surface of metal oxide and hence its sensing
characteristics [36].
1.3. Thin film based sensors
In the recent past, synthesis of nanostructured metal
oxide thin films with and without the doping elements has
been reported to obtain smaller grain size [37]. Thin films with
smaller grain size are favorable as the increased surface to
volume ratio, carrier concentration and enhanced catalytic
activity, facilitate its interaction with larger number of gas
molecules.
The thin film formation process involves several steps
such as thermal accommodation, adsorption of metal atoms on
the substrate and nucleation followed by crystallization or the
formation of microstructure. Thus, the thin films synthesized
from the techniques like paste/slurry, chemical and physical
vapour deposition techniques, etc. [37–40], result in different
electrical, optical and magnetic properties. In each case,
growth process (assembly of molecular building blocks) is
different leading to variance in nucleation, growth direction,
crystallographic orientation (atomic stacking energy), packing
density, interfacial energy and diameter of the crystallites. To
date, thin film technology has been either empirical or semi-
empirical. Although basic research in understanding and
relating several growth parameters has been reported [41,42],
www.cognizure.com/pubs
Science Letters Journal
it would take decades of research to have a complete
understanding and precise control of the thin film growth.
Besides the nature and properties of the thin film, the
environmental conditions such as operating temperature and
humidity determine the sensing performance and
characteristics of the thin film gas sensors. The operating
temperature influences the receptor function through its effect
on the chemical dynamics at gas-solid interface and thus
determines the important sensing properties such as response,
selectivity, stability, response and recovery times [36]. In
addition, humidity level in the atmosphere has a larger
influence on the sensor response [21], as the water vapour
absorbed on the metal oxide surface affects the electronic and
ionic conducting properties of the semiconducting metal
oxides. The review articles published so far have focused on
specific aspects such as general gas sensing principles
[20,35,43–51], response and conduction mechanisms [52–57],
influence of structural parameters [58], nanostructures
[28,29,34,39,59–65], environmental gases [22,31,66,67], and
the theory behind the gas sensing principle [44,68–70].
Although, numerous research articles have been published on
thin film based gas sensors, greater attention is required on the
sensing behaviour of metal oxide materials especially of thin
film form, the relation between sensing characteristics and the
most influencing parameters namely the operating
temperature, type and concentration of gas molecules. Hence,
in this review, we address the REDOX mechanisms associated
with the interactions of metal oxide thin films of both n- and p-
type conductivities for the selected oxidizing and reducing gas
molecules of different concentrations in dry and wet
atmospheric conditions. For this review, the most toxic,
combustible and hazardous gases such as CO, CO2, NO2, SO2,
NH3, H2S and C2H5OH have been considered. And the
considered base materials are zinc oxide (ZnO), tin oxide
(SnO2), indium oxide (In2O3), tungsten trioxide (WO3) and
copper oxide (CuO), nickel oxide (NiO) as examples of n-type
and p-type semiconductors respectively.
2. Role of ambient atmosphere
Receptor function, first phase of sensing
phenomenon, is a chemical process between target gas in the
atmosphere and metal oxide surface. The atmosphere is
composed of many gases; some of which aid, impede, or have
negligible effect on the receptor function. The lower layer of
atmosphere is mainly composed of nitrogen, oxygen and water
besides traces of other gases. The ambient of a metal oxide
surface while sensing is normally classified as dry and wet,
based upon the humidity level. As will be discussed, in wet
atmosphere, water molecules have a major role and influence
on the receptor function while oxygen plays a decisive role in
the dry atmosphere. The dense water molecules and high
electronegativity of oxygen can make them easily adsorbed by
the metal oxide surface, as electron acceptor. Similarly, the
interaction of target gas with metal oxide would cause changes
in the resistance of the metal oxide. Therefore, the response of
metal oxide towards a specific target gas is net change in
resistance produced due to gas-solid interaction in the ambient
atmosphere. Thus, the response of a metal oxide surface
strongly depends on the composition of atmosphere; especially
water (wet atmosphere) and oxygen (dry atmosphere) which
defines the baseline for the sensor response and calibration.
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
Rapid industrial growth and increase in automobiles
have led to drastic intensification in the concentration of toxic,
hazardous and greenhouse gases in the atmosphere. These
gases can be extremely dangerous and life threatening when
the concentration levels exceed the threshold [22]. In the
context of receptor mechanism of metal oxide based gas
sensors, these gases can be classified as oxidizing (eg. CO2,
NO2) and reducing (eg. CO, SO2, NH3, H2S, C2H5OH) gases.
The interaction of each of these gases with metal oxides will
be discussed separately in the following sections.
2.1. Wet atmosphere
Humidity poses a great challenge in the metal oxide
based gas sensors. In many cases, increase of humidity in the
atmosphere greatly impedes the response of sensor [21,71].
The water undergoes dissociative adsorption on metal oxide
surfaces as given in Eq. 1 and the resultant ions will be
adsorbed on the metal oxide surface [72].
(1)
In wet atmosphere, ratio of water molecules to active
sites (metal in metal oxide) decides the adsorption mechanism.
Chemisorption mechanism is followed at low humidity level
while physisorption is observed at higher levels of humidity.
Heiland and Kohl [73] proposed two possible
mechanisms for explaining the effect of humidity on metal
oxide surfaces, which were subsequently verified
experimentally [21,74,75] using the tin oxide material. As
shown in Figure 2 and Eqs. 2 and 3, the mechanisms were
simply based on the number of water molecules interacting
with each lattice site on the metal oxide surface.
( )
(2)
( )
(3)
Figure 2(a) and Eq. 2 corresponds to a case of a water
molecule interacting with two metal oxides, where two Sn-OH
dipoles are formed from the dissociated hydroxyl ion and by
combination of hydrogen ion and a lattice oxygen. Two free
electrons are produced from each oxygen vacancy ( ) in the
lattice during the formation of Sn-OH bond. On the other hand,
if each water molecule interacts with only a single metal oxide
as shown in Figure 2(b) and Eq. 3, while, the dissociated
hydroxyl ions are bonded with each metal site, the hydrogen
ion diffuses into the lattice to bind with lattice oxygen, thus
forming two hydroxyl bonds per metal site. The rooted OH
group acts as a donor due to lower electron affinity and
ionization. Therefore, irrespective of the mechanism,
adsorption of water molecules on the metal oxide surface
changes the sensing properties of the metal oxide surface. It
may be due to the change in conductivity from the free
electrons produced or change in the electron affinity due to the
deep-rooted hydroxyl bonds or simply by the occupation of the
active sites by the adsorbed water molecules.
Morrison [76], Henrich and Cox [77] have suggested
another possible mechanism, co-adsorption of water molecules
on the other adsorbate. It seems to be a formation of water
vapour layer on the surface due to higher humidity level.
Figure 3 shows the schematic representation of humidity
sensing by metal oxide surface, described by Kannan et al.
3
 Science Letters Journal Sci. Lett. J. 2015, 4: 126

Figure 2. Mechanisms of humidity adsorption on the surface of tin oxide; (a) one water molecule for two metal sites and (b) one water
molecule per metal site.

Figure 3. Schematic representation of humidity sensing at ZnO (Reprinted with permission from Ref. [75] Kannan et al. Sens. Actuat. A
164 (2010) 8. © Elsevier Publishing).

[75]. It explains that, at low humidity, adsorption of water
molecules on the metal oxide surface obeys chemisorption
process as explained by Eq. 2 and 3 and at higher humidity
levels, all the active sites on metal oxide surface are occupied
by water molecules and later it can be formed as an additional
layer on the surface following the physisorption process. The
free movement of proton occurs along the water layer as
shown in Figure 3 and during physisorption process, resistance
of the film is decreased. Further increase in humidity leads to
co-adsorption where the water molecules try to dislodge the
adsorbents occupying the active sites. During the
chemisorption, resistance drastically decreases while it is being
slowed down during physisorption at higher humidity level
and the conductivity changes almost ceased during co-
adsorption at much higher humidity levels. Author has
reported that physisorption leads to capillary condensation and
the conduction process mainly follows Grotthuss transport
mechanism [75,78].
Bai et al. [21] have observed an increase in the
resistance of ZnO nanostructured thin films for relative
humidity (RH) levels from 10-75% and a decrease at higher
4 Cognizure
© Cognizure. All rights reserved.
humidity levels, which is characteristic p-type behaviour.
However, Kannan et al. [75] have reported a decrease in
resistance, indicating n-type behaviour. Figure 4 shows a
comparison of the resistance variation of ZnO films with
humidity reported by these authors. The approximate linear
change in resistance with humidity up to 75% of RH in either
cases show the donor behaviour of water molecules followed
by chemisorption explained by the Eq. 2 & 3 and Figure 2. The
abrupt change in resistance at RH above 75% is because of the
co-adsorption mechanism suggested by Morrison, Henrich and
Cox. Bai et al. [21] and Hotovy et al. [79] have reported that
RH around 50% is optimum for sensing gases by both n and p
- type materials. Since humidity severely affects the sensing
response of metal oxides towards gas molecules, it is
customary to study and optimize the effect of humidity in the
design and development of metal oxide based gas sensors.
2.2. Dry atmosphere
The atmosphere with RH less than 20% humidity is
termed as dry atmosphere. Apart from humidity, other
components in the atmosphere such as nitrogen (N 2) and
www.cognizure.com/pubs
Science Letters Journal
Figure 4. Resistance vs. Relative Humidity plot for n-type [75] and p-type [21] ZnO metal oxide thin films.
oxygen (O2) has a characteristic influence on the gas-solid
interaction. In the following section, the role of these
atmospheric gases in the sensing characteristics of metal
oxides has been discussed.
2.2.1. Nitrogen (N2)
The molecular nitrogen is the most abundant gas in
atmosphere, but it is chemically non-reactive with other gas
molecules and metal oxide surface. The triple bond in the
molecular nitrogen makes it a strong and chemically inactive
gas, as it requires more energy to break its bonds. Hao et al.
[80] demonstrated the chemical inactivity of nitrogen gas with
p-type semiconducting copper oxide. CuO thin film showed an
increase in electrical resistance when reacted with reducing
gas. When reducing gas was replaced gradually by nitrogen,
then there was no change in the resistance besides the
reduction in resistance due to desorption of the reducing gas
molecules, proving the inertness of the nitrogen gas.
Therefore, nitrogen is often used as carrier gas to study the
chemical kinetics of the interaction between a test gas and the
metal oxide surface.
2.2.2. Oxygen (O2)
In the atmosphere, oxygen is the second largest
element after nitrogen. Oxygen plays a predominant role in the
adsorption process due to its high electronegativity of about
3.65 and lone pairs of electrons, making it easily adsorbed on
the surface of metal oxides. Diatomic oxygen is a non-reactive
species in the gas phase, while interacting with the metal oxide
surface, it act as an electron acceptor and gets ionized [81] and
form an ionic layer on the surface. This helps in sorption of
other gas molecules on to the metal oxide surface. In dry
atmosphere, chemisorbed oxygen molecule strongly influenced
the receptor function. Thus, the principle of metal oxide gas
sensor mainly depends upon the oxygen concentration and its
rate of adsorption and desorption. During the adsorption
process, the oxygen molecule gains an electron from the metal
oxide surface and turned to ionic form ( ) [82]. Thus
electrons trapped on the surface of grains, and results in the
increase of the width of space charge region and hence the
height of potential barrier. This, in turn, reduces the
conduction of electron between the grains, which influence the
transduction process of the metal oxide surface. In addition,
the grain boundary resistance also plays a crucial role in
determining the surface resistance of the sensing element.
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
Thus, the adsorption and desorption of oxygen molecules is
associated with corresponding changes in the resistance
measured on the metal oxide surface. The chemisorption
process of oxygen on the metal oxide surface can be described
as given in Eq. 4 [57]. It can be seen that the concentration of
electrons on the metal oxide surface acts as an active site for
the oxygen adsorption. The number of electrons gained by the
oxygen (O2) during the adsorption decides the ionic strength
( ) of the adsorbed species ( ). Barsan and Weimer
[57] and Yamazoe et al. [15] reported that at higher
temperatures, molecular species turn to atomic; either lattice
( ) or dissociative ( ), which can also be effectively
enhanced by catalysts or dopants [20].
(4)
The following Eq. 5 describes the adsorption process
in the case of oxygen deficient sites ) on the metal oxide
surface. Oxygen from the ambient diffuses to the oxygen
vacant sites in metal oxide surface, by consuming one or two
free electrons. Thus, the chemisorption of oxygen molecules
reduces the mobility of electrons leading to reduction in
conductance in n-type materials as well as reduces the active
sites for further adsorption.
(5)
2.3. Reduction-Oxidation (REDOX) mechanisms for
oxidizing and reducing gas molecules
2.3.1. Oxidizing gases
2.3.1.1. Oxygen (O2)
In the context of REDOX mechanisms, gases such as
O2, NO2, CO2 which have the tendency to accept electrons
from the metal oxide surface, are termed as oxidizing gases.
Oxygen is the dominant one among oxidizing gases, which
adsorbs quickly with metal oxide surfaces compared to others.
The adsorption can be enhanced by increasing the operating
temperature, using dopants and by reducing the grain size [20].
Below the temperature of 200 °C, O2 can accept one electron
and above 200 °C, it can accept two electrons from the metal
oxide surface, and it is given in the Eqs. 6 and 7 [15,78]. The
adsorbed oxygen molecules/atoms are desorbed quickly, when
interacts with other gas molecules.
5
 Science Letters Journal
(6)
} (7)
2.3.1.2. Carbon dioxide (CO2)
The linear bonded atoms of carbon dioxide (CO 2)
molecule have stable structure and there is no lone pair of
electrons to bond. Ostrick et al. [83] have reported that at low
temperatures the dissociated hydroxyl and hydrogen ions from
water molecules at the surface of metal oxide react with
gaseous CO2 to form carbonate ions as given in Eqs. 8-
11, with the intermediate products, formate ions and
bicarbonate ions [72]. At high temperatures, CO2 molecules
interact with the layered oxygen ions ( to directly form
carbonate ions [84] as given in Eq. 12. Thus, the consumption
of electrons by each CO2 molecule during its interaction with
the metal oxide surface leads to reduction in conduction, which
can be used for sensing CO2.
(8)
(9)
(10)
(11)
(12)
The observed chemical kinetics of CO2 molecule
interaction is in close agreement with CdO nanostructured thin
film [85]. However, Kim and co-workers [71] have reported
the CO2 detection behaviour of lanthanum coated tin oxide in
the ambient of dry air, pure oxygen, nitrogen as well as in wet
atmosphere. Lanthanum coated tin oxide showed better
sensing performance in the oxygen atmosphere, compared to
others, while worst performance at the higher relative humidity
level. Besides the oxygen adsorption, CO2 molecules further
oxidized the metal oxide surface and increase the surface
resistance. Here the interaction of stable CO2 on the surface
achieved might be the existence of the additive lanthanum
present on the surface [71]. Based on the results, the following
REDOX mechanism is proposed to explain the interaction of
oxygen and CO2 on the metal oxide surface.
(13)
2.3.1.3. Nitrogen dioxide (NO2)
Nitrogen dioxide is a strong oxidizing agent and has
strong electrophilic property [86], which makes this molecule
to be quickly adsorbed on the metal oxide surface. NO 2 can
react with metal oxide surface both in the presence and
absence of oxygen as given in the Eqs. 14 and 15 [87]. It can
be seen that the oxidation of NO2 leads to the reduction of
conduction electrons in the conduction band.
(14)
(15)
6 Cognizure
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
If the metal oxide thin film has oxygen vacancy in the
surface, nitrogen dioxide turns to nitrogen monoxide (NO) by
loss of one oxygen atom as given in Eqs. 16 and 17 to vacant
site in the metal oxide surface. The adsorption of oxygen from
the NO2 molecule on to the vacant site leads to decrease in
conductance of the n-type metal oxide [88]. X-ray
photoelectron spectroscopy (XPS) studies revealed the reaction
mechanism described in Eq. 18 of interaction of NO 2 gas
molecules with In2O3 surface [89] and the same phenomena
was described with Au doped WO3 thin film [90]. Eq. 18
explains that NO2 directly adsorbed on the metal sites by
electron capture and desorbed as NO [91].
(16)
( ) (17)
→ →
}
→
(18)
2.3.2. Reducing gases
Reducing gases are those, which act as electron
donors when interacting with metal oxide surface. During this
interaction, reducing gases desorb or remove the chemisorbed
oxygen ions and physisorbed hydroxyl ions from the metal
oxide surface. The variation in the resistance of the material is
used to detect the concentration of reducing gases such as SO 2,
CO, H2, NH3, H2S and C2H5OH by the chemical changes
following REDOX reaction.
2.3.2.1. Sulfur dioxide (SO2)
Sulfur dioxide is one of the most toxic gases that
makes the metal layer non-resistant by bonding with its strong
electron pairs. Normally NO2, SO2 reacts with water molecules
to form an acid in atmosphere that is given in Eq. 19.
(19)
In the wet atmosphere, hydroxide ions and SO2 make
a surface more acidic, it strongly corrodes the material. At low
humidity or dry atmosphere, SO2 molecules interact with
adsorbed oxygen on the surface to form sulfate (SO 4) ions and
it increases the conductance of the n-type material. Further, the
continuous interaction of SO2 molecules directly bond with
metal sites by completely desorbing the adsorbed oxygen from
the surface and continues to replace the lattice oxygen from the
first layer, and after the incorporation the resistance of it
remains constant. The proposed mechanism is given in Eqs. 20
and 21.
(20)
(21)
Rodriguez et al. [92] and Kim [93] investigated the
adsorption of SO2 on the ZnO and NiO surface. In ZnO,
formation of sulfite and sulfate on the surface was confirmed
by XPS analysis. NiO material also showed the same process
and both the studies revealed the formation of sulfate, Eq. 22
explains the adsorption and desorption of SO2 on ZnO
material, the same process followed in NiO sample. If, oxygen
vacancy or available metal (M) sites are more in the metal
oxide surface, then SO2 molecules react with the active sites
and forms sulfur and oxygen ( ). In n-type
www.cognizure.com/pubs
Science Letters Journal
Figure 5. CO gas – SnO2 solid interaction mechanism at ambient temperature (Reprinted with permission from Ref. [74] Barsan et al.,
Fresenius. J. Anal. Chem. 365 (1999) 287. © Springer-Verlag).
material, chemical kinetics of SO2 molecules increases the
carrier concentration and it is due to the replacement of sulfate
molecules on the surface instead of oxide ions [92].
(22)
2.3.2.2. Carbon monoxide (CO)
CO acts as a reducing agent, the oxidation of carbon
monoxide increases the electron concentration on the surface.
In dry atmosphere, carbon monoxide reacts with chemisorbed
oxygen to form carbon dioxide. In wet atmosphere, metal
oxide does not respond to lesser concentration of carbon
monoxide like in dry atmosphere. Under this situation, metal
oxide surface led to the formation of formate (HCO2) ions,
which is an intermediate during the oxidation of CO. There are
experimental and theoretical results/analysis that proposes the
REDOX mechanism given in Eqs. 23 and 24 [72] (Figure 5).
Weimer group investigated the interaction between the p-type
CuO with CO, in the presence and absence of humidity, by
using the work function calculation and compared with the
experimental work. He observed that the presence of humidity
increased the response of metal oxide [94].
(23)
(24)
The detection of CO by metal oxide semiconductor in
oxygen atmosphere is better than nitrogen and wet atmosphere
[24]. Hubner et al. [95] showed the formation of carbon
dioxide as a residue, during the interaction of carbon monoxide
on the surface of WO3. When the operating temperature is
below and above 250 °C, then the REDOX mechanism follows
the Eqs. 25 [96] and 26 [24] respectively. Both the equations
confirm that, operating temperature determines the limit of
detection for specific materials.
(25)
(26)
2.3.2.3. Hydrogen (H2)
H2 molecules are adsorbed as protons on the thin film
surface and desorbed as water vapour [72], and again interacts
with the surface as hydroxyl ions. Above 300 °C, hydrogen
and water vapour can be evolved completely [59].
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
(27)
Adsorption of protons on the surface, enhance the
electron concentration, which is given in Eq. 27. The detection
of hydrogen in the oxygen atmosphere may follow the Eqs. 28
and 29. From these equations, one can determine the detecting
limit of the metal oxide; hence, detection limit is associated
with oxygen adsorption and operating temperature. Hao et al.
[80] have showed the detection of hydrogen using p-type CuO
metal oxide and the reaction is depicted in Eq. 28.
(28)
(29)
2.3.2.4. Hydrogen sulfide (H2S)
In the metal oxide surface, H2S vapour strongly reacts
with the metals to form elemental sulfur. Oxygen adsorption
on the metal oxide surface promotes the response of H2S
vapour, that is presumed by XPS studies and described in Eq.
30 [97].
(30)
The presence of H2S on the metal oxide surface can
be confirmed by three possibilities [98].
Eq. 30 explains the strong reduction behaviour that
happens in dense oxygen atmosphere along with the bi-product
of sulfur dioxide and water vapour.
At low partial pressure of oxygen, H2S directly reacts
with lattice oxygen to form SO4 and produces the oxygen
vacancy in the surface of the metal oxide which, in turn,
increases the conductance as given in the Eq. 31 and this
process has been explained with the help of in situ XPS [99],
(31)
where denotes electrically neutral oxygen atoms in their
lattice.
At zilch of oxygen in the atmosphere or after
continuous interaction of H2S on the surface, adsorbed oxygen
were completely desorbed and it led to direct interaction with
the surface and results in the formation of elemental sulfur.
This sulfur can replace the lattice oxygen and the obtained
7
 Science Letters Journal
Figure 6. H2S gas sensing mechanism on copper oxide thin film (Reprinted with permission from Ref. [101] Ramgir et al., Sens. Actuat. B
151 (2010) 90. © Elsevier Publishing).
reaction is said to be sulfurization reaction, which is given in
Eqs. 32 and 33.
(32)
(33)
In situ Raman and impedance measurements also
reveal the same reaction of sulfurization with tin oxide
[98,100]. This same reaction was observed in the CuO thin
film, ( ), where copper sulfide
turned back to copper oxide when reacted with oxygen
( ) [101]. In WO3 material, wet
atmosphere did not affect the response of H2S. It was shown
that, 90% of RH slightly decreases the response value to
~20% of total response [102].
The following reaction scheme (Figure 6) and the
resultant band bending sequence depicts the hydrogen sulphide
interaction with CuO.
2.3.2.5. Ammonia (NH3)
The lone pair of electrons of NH3 provide strong
electron acceptor behaviour. But it acts as an electron donor to
the metal oxide, when reacted with the adsorbed oxygen ions
on the surface by reverting the trapped electrons. Nguyen et al.
[103] proposed the mechanism that generates free electrons
accomplished by the number of oxygen ions reacted with NH 3
molecules, given in the Eqs. 34-36. Eq. 34 has been adopted
by most of the authors [104–108].
} (34)
(35)
(36)
In humid atmosphere, the kind of reactions that takes
place on the surface, which would modify its resistance are yet
to be investigated. However up to 60 and 72% of RH did not
affect the sensing performance of the sensor [105,109].
2.3.2.6. Ethanol (C2H5OH)
Ethanol is the most important organic molecule to be
detected in the ambient since it is being used in many
8 Cognizure
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
laboratories and industries for various research purposes and
applications. Based on whether the surface of metal oxide is
acidic or basic, functional group of the adsorbed ethanol
dissociates as water vapour or hydrogen molecule.
Dissociation into water vapour (dehydration) or hydrogen
molecule (dehydrogenation) process led to desorption of
carbon dioxide gas molecule and water vapour via the
formation of cyclobutadiene (C2H4) and acetaldehyde
(CH3CHO). Also, desorption of ethanol was determined by the
partial pressure of oxygen in the ambient atmosphere. Cyclic
process of ethanol adsorption reduces the oxygen content in
the atmosphere, hence the intermediate products react with the
lattice oxygen in the metal oxide surface, and creates oxygen
vacancies in the lattice and these process are given in Eqs. 37-
41 [96,110–116]. These REDOX mechanism process increases
the electron concentration in metal oxide surface by desorption
of oxygen from the surface and lattice. However, the in-situ
gas chromatography study of ethanol reaction with metal oxide
material revealed the desorption of carbon dioxide from the
surface [117].
(37)
(38)
(39)
(40)
(41)
By the adsorption of dissociated H and OH ions on
the oxygen adsorbed surface of the metal oxide can modify the
surface to be acidic or basic nature. At low humidity level
(36%) lack of hydroxyl ions lead to follow the Eqs. 37 and 38,
while at higher humidity (96%), the mechanism will follow the
Eqs. 39 and 40, because of enhancement of hydroxyl ion
concentration. The infrared spectrum analysis confirmed that
50% of RH has not affected on the response of the sensor [21].
3. Role of metal oxides
Metal oxide materials are the main source of gas
sensor industry. The investigations on metal oxide revolve
around studying their properties and methods of increasing the
sensitivity and selectivity towards specific gases at different
operating conditions. Specific metal oxides such as, Cr 2O3,
Mn2O3, Co3O4, NiO, CuO, SrO, In2O3, WO3, TiO2, V2O3,
www.cognizure.com/pubs
Science Letters Journal
Figure 7. Surface morphology of (a) ZnO nanotetrapods, (b)
nanowires, (c) nanobelts and (d) tetrapods film deposited on
alumina substrate. Isolated nanostructures aligned between gold
electrodes with 25 µm separation: (e) three nanowires/belts
shown by arrows and (f) a nanobelt (Reprinted with permission
from Ref. [129] Gupta et al., J. Chem. Sci. 122 (2010) 57. ©
Springer-Verlag).
Fe2O3, GeO2, Nb2O5, MoO3, Ta2O5, La2O3, CeO2, Nd2O3, ZnO,
Ga2O3 and SnO2 are suitable for sensing because of their
electronic structure [61]. The metal oxides can be classified as
n-type and p-type based on the majority charge carriers. The n-
type (ZnO, SnO2, In2O3 and WO3) and p-type (NiO and CuO)
are the most promising materials in sensing applications. In
this section, the performance of these metal oxides towards
selected toxic gases; NO2, SO2, CO2, H2S, SO2, CO and
C2H5OH have been discussed.
3.1. n-type metal oxide
3.1.1. Zinc oxide (ZnO)
Zinc oxide is a versatile material among the metal
oxides and is used for several applications [118]. In gas
sensing applications, its n-type semiconducting property,
chemical stability, tunable transport properties, large exciton
binding energy have made it as one of the most promising
candidate. Sensing CO2 in the atmosphere using metal oxide
materials is a challenging process since the sensing mechanism
is based on the reactivity of the target gas. Even though, few
metal oxide sensors including ZnO have been reported for
sensing CO2, their sensitivity is found to be low and to date the
underlying sensing mechanism is not known clearly. The
reactive sputter deposited ZnO thin film at the substrate
temperature of 403 K showed a good response of 2.17 at room
temperature towards CO2 gas. The highly oriented (111) plane
and the grain size of ~20 nm might be the reason for sensing
CO2 gas [119]. NO2 can be sensed by, ZnO based thin film
sensors with different morphologies synthesized using physical
and chemical vapour deposition methods [120–125] were
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
reported. These sensors showed a considerable response only
at the elevated operating temperatures. Noticeably, spray
pyrolysis deposited nanostructured ZnO thin film showed a
response of 40 towards 0.6 ppm concentration of NO 2 gas at an
operating temperature of 135 °C [87]. This is one of the best
NO2 sensors in detecting the lowest concentration. The
response of ZnO thin film to SO2 gas was found to be 3 at
300 °C [124]. Hierarchically porous ZnO nanosheets [126]
prepared using solvothermal method showed a response of
11.7 for 100 ppm of CO at 300 °C while ZnO thin film
deposited by atomic layer deposition technique showed an
appreciable response at room temperature [127] itself. These
results imply that the deposition methods could decide the
sensing characteristics of the materials. Though there are many
ZnO gas sensors available for sensing ammonia gas, majority
of them can sense only at the elevated operating temperatures
such as 200 °C [123] and 300 °C [105]. But recently our group
has reported a spray pyrolysis deposited nanostructured
undoped [109] and doped [128] ZnO thin films which showed
an excellent response of 233 and 2667 towards 25 ppm and 50
ppm of ammonia vapour at room temperature respectively.
Various forms of ZnO nanostructures namely nanowire,
nanorod, nanobelt, tetrapod structures and also single nanowire
shown in Figure 7 were considered for fabricating H2S sensors
[129]. Among them, ZnO nanowires showed good response
towards H2S and NO gases. Better response towards H2S
might be due to the change in grain boundary resistance, while
intra-grain resistance accompanied with grain boundary
resistance for NO. This was supported by the electrical
transport mechanism studied using impedance spectroscopy
measurements. However, ZnO nanorods synthesized by
hydrothermal method showed a peculiar H2S sensing
characteristics [130]. In this case, nanorods detected the
presence of 0.05 ppm of H2S at room temperature (~24 °C).
The same material effectively sensed 1 ppm of C2H5OH at
elevated temperature of 350 °C with better selectivity. Though
there are many ZnO based ethanol sensors, many of them have
shown better response only at the elevated operating
temperatures [113,117,124,130–134] and very few reports are
available for sensing ethanol at room temperature [135,136].
Our group has recently reported a room temperature ethanol
sensor using spray pyrolysis deposited nanostructured ZnO
thin film [137]. From these observations, one can understand
the role of nanostructures, grain size, grain boundary
resistance, operating temperature in fabricating gas sensors for
different vapours/gases.
3.1.2. Tin dioxide (SnO2)
The n-type semiconducting and wide band gap
material namely SnO2 is one of the most exploited materials by
the gas sensor industries. Since 1968, SnO2 has been
dominating in the design of Taguchi commercial gas sensors.
RF sputtered SnO2 thin film with rough and porous micro
surface showed a considerable response towards 1 ppm of NO2
gas [91] at 100 °C. This was achieved because of the number
of free Sn sites available on the porous surface which in turn
depends on the growth kinetics during deposition and
adsorption of oxygen ions on the surface. Electrostatic spray
deposited SnO2 film showed a response of 1 for 20 ppm of
SO2 at 100 °C [138]. Since the highly stable CO2 gas showed
poor response when reacted with pure SnO2 metal oxide film,
researchers prepared doped SnO2 films as well as with
catalytic coatings to solve this very challenge. The catalyst
9
 Science Letters Journal
Figure 8. (a) TEM image of SnO2 (a) nanoparticles, (b) nanorods and (c) nanoflowers (Reprinted with permission from Ref. [105] Rout et
al., Nanotechnology 18 (2007) 205504. © IOP Publishing Ltd.).
Figure 9. SE micrograph of the (a) undoped In2O3 base film and
(b) Au activated In2O3 film (Reprinted with permission from Ref.
[145] Steffes et al., Sens. Actuat. B 78 (2001) 106. © Elsevier
Publishing).
lanthanum treated SnO2 thick film showed a response of 1.38
for 2000 ppm of CO2 at 400 °C in the atmospheric condition
[71]. Similarly, SnO2/Al2O3 combination showed a good
response to CO2 gas [139]. Dip coated SnO2 thin films with
different processing times showed a marked difference in the
response characteristics of H2S detection. The response of thin
films synthesized with 1 hr stirring process showed a response
of ~400 for 68.5 ppm of H2S gas at 30 °C [140] while, the
samples made with 5 hr stirring process showed a response of
81 for 3.4 ppm (lowest possible detection) at ~30 °C [141].
Hence the figure of merits of the gas sensors can be tuned by
varying the synthesis processing. The thick film ammonia
sensor was fabricated using SnO2 nanoparticles, nanorods and
nanoflowers as shown in Figure 8 [105]. Among them thick
film SnO2 nanoflowers showed good response and response
and recovery time. It might be due to the higher surface area
relative to nanoparticle and nanorod structures. It is highly
selective towards ammonia, than compared to H2, H2S and CO
gases.
But these nanostructured materials showed no
response for SO2. SnO2 thin films with different thickness
prepared using atomic layer deposition (ALD) technique [142]
showed the response of ~31 towards CO gas at 250 °C. Since
the generation and transduction of free electrons were the
prerequisite of sensor material, developed thin film with
particular thickness and temperature yielded the maximum
response. The nanocrystalline SnO2 powder with a grain size
of 8 nm and surface area of 214 m2 g-1 prepared using
10
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
homogeneous precipitation ethanol-thermal method showed a
response of 25.8 towards 80 ppm of ethanol at room
temperature [143]. The similar nanocrystalline SnO2 grains
with size of ~ 6 nm synthesized by ultra-sonic spray pyrolysis
technique showed a response of 491 at an operating
temperature of 300 °C and possessed selectivity in the mixture
of methanol and isopropanol [114]. Surface modification by
altering the synthesis methods produced a different sensing
response.
3.1.3. Indium oxide (In2O3)
Indium oxide is an n-type semiconducting material
with direct band gap of 3.6 eV and indirect band gap of about
2.6 eV. It has been widely investigated next to SnO 2 and ZnO
in gas sensing applications. In2O3 thin film based NO2 sensors
were fabricated using sol-gel and electron-beam (EB)
techniques with 5, 6, 20 and 100 nm grain sizes respectively
[144]. Thin film with 5 nm grain size showed a response of 60
for 1 ppm of NO2 at 150 °C. Authors have highlighted the role
of agglomeration of particles, smaller crystallite and grain size
in sensing NO2 gas. Steffes et al. [145] reported that RF
magnetron sputtered Au doped In2O3 thin films showed better
response towards SO2 gas than undoped In2O3. Figure 9 shows
the Au activated surface of the doped In2O3 film morphology.
Compared with pure In2O3, Au modified film exhibited better
sensing properties because of the increased number of active
sites. It also modified the electronic structure and made the
thin film surface capable of interacting with SO2 molecule.
The influence of operating temperature was absent in the SO 2
sensing characteristics of Au modified In2O3 thin films.
Mesoporous In2O3 nanofibers were prepared using
unique and cost-effective electro-spinning technique which
exhibited a response of ~530 for 100 ppm of CO gas in air
atmosphere at 300 °C [146]. The Brunauer-Emmett-Teller
(BET) investigation unveiled that the sample had highest
surface area (48 m2 g-1) and pore diameter (10.3 nm) which, in
turn, resulted in a strong sensing of CO. While sensing
ammonia vapour, sol-gel synthesized In2O3 nanorods and
nanoparticles showed the response of ~20 and ~40 towards 80
ppm at 300 °C [105]. In2O3 nanocrystals synthesized by
hydrothermal and chemical precipitation method [97] were
used to detect H2S. The response was found to be good with
better selectivity in the presence of 11 gases [97]. Kulkarni and
Borse [147] investigated the CO gas sensing performance of
In2O3 thick films synthesized by screen printing method. Their
sensor showed response towards the 500 ppm of a wide range
of gases like carbon dioxide, ethanol, ammonia, and liquefied
petroleum at 250-300 °C. At the same time it showed a
considerable response towards 100 ppm of hydrogen sulfide
Cognizure
www.cognizure.com/pubs
Science Letters Journal
Figure 10. Polyhedral representation of the structure of
orthorhombic β-WO3 looking down the (a) [100], (b) [010], and
(c) [001] directions, and tetragonal α-WO3 looking down the (d)
[100], (e) [111], and (f) [001] directions (Reprinted with
permission from Ref. [159] Vogt et al., J. Solid State Chem. 144
(1999) 209. © Elsevier Publishing).
gas at 150 °C. In this work the significance of operating
temperature was emphasized in determining the sensing
response. In2O3 nanocrystals synthesized by wet chemical
method, showed a linear response for 1 to 100 ppm of ethanol
at 200 °C [148]. Authors have emphasized the sensing
behaviour due to the large contact area exhibit by face contacts
between the nanocrystals. This result was found to be in
drastic contrast in the case of nanowire and nanorod structures
with point contacts [148].
3.1.4. Tungsten trioxide (WO3)
WO3, an n-type semiconducting material having band
gap of 2.7 eV attracted researchers to investigate its sensing
properties. „W‟ sites with different oxidation states of the non-
stoichiometric WO3 triggered the researchers to investigate the
chemistry of the surface reactions. The first investigation by
Sbervegleri et al. [149] on the response of WO3 towards NOx
was an eye opener to use the same material for various gas
sensing studies. NO2 sensor using WO3 thin film was
fabricated by modifying the surface area by varying the
discharge gas in reactive sputtering technique [150]. These
sensing elements with porous morphology and high effective
surface area exhibited a maximum response of ~450 towards
one ppm of NO2 at 200 °C. Similarly, mesoporous structured
WO3 thin film synthesized by low frequency AC
electrophoretic method was used to detect 100 ppb of NO 2 gas
at 200 °C [151]. In a different way, WO3 films with
agglomerated grains prepared using thermal evaporation
technique showed a significant response towards 100 ppb of
NO2 at 100 °C [152]. These studies have strongly revealed the
role of enhanced surface area and hence the receptor function
of the sensing elements and at the same time, the agglomerated
grains mended the transduction function. Because of the very
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
Figure 11. Unit cell structure of cupric (CuO) and cuprous
(Cu2O) oxide (Reprinted with permission from Ref. [160] Pike et
al., Appl. Catal. A Gen. 303 (2006) 273. © Elsevier Publishing).
poor response of In2O3 film towards CO2 and SO2, it is hard to
find reports on In2O3. WO3 films synthesized by electro-
spinning method showed a response of ~1.5 for 100 ppm of
CO2 [153] and films developed by electrostatic deposition
method showed a response of ~1 for 10 ppm of SO 2 at 200 °C
[154]. WO3 films prepared using thermal deposition showed
comparatively a better response of 18.2 for 10 ppm of
ammonia vapour at 200 °C [152] than sensors synthesized by
other methods [90,108,151,153,155,156]. Noticeably, thermal
vapour deposited WO3 undoped and Pt sensitized nanorods
showed a better response towards CO gas [157]. The response
was enhanced when the sensing layer was functionalized with
Pt nanoparticles. Pt nanoparticles enhanced the active sites,
and ultimately enhance the redox reaction rate. Nanocrystalline
WO3 thick films showed an excellent response towards H2S at
room temperature [158]. The observed room temperature
sensing behaviour for 10 ppm of H2S with the remarkable
response of ~104 might be due to the presence of grains with
the tetragonal phase. The tetragonal phase of WO3 (Figure 10
a-c) was obtained by sintering the ultra-fine powder at 500 °C,
and it was found that 500 °C is the optimum sintering
temperature. However, the orthorhombic WO3 (Figure 10 d-f)
thin film with nanosheet morphology was synthesized by a
simple sonochemical method showed a response of 15.6
towards 100 ppm of ethanol [155]. Figure 10 depicts the
tetragonal and orthorhombic crystal planes of WO 3 [159].
These results have highlighted the role of tetragonal [158] and
orthorhombic [155] crystal phases of WO3 in tuning the
selectivity of the sensor.
3.2. p-type metal oxide
3.2.1. Copper oxide (CuO)
Copper oxide, a p-type material exists as cupric
(CuO) and cuprous (Cu2O) oxide with narrow band gap of 1.2
– 1.5 eV and 2.12 eV respectively. The exchange of oxygen
from atmosphere and lattice oxygen vacancy during the
sensing process, switches cupric to cuprous and vice versa.
Figure 11 shows the unit cell structure of cupric and cuprous
oxide material [160]. This transformation plays a vital role in
the chemical kinetics of gas – solid interaction.
Nanocrystalline CuO thin film with monoclinic
crystal structure synthesized by sol-gel method was used to
detect both the oxidizing and reducing gases [161]. While
11
 Science Letters Journal
Figure 12. Plan view of (a) hollow NiO hemispheres and (b) 2-D
hexagonal close-packed arrays of hollow NiO hemispheres
(Reprinted with permission from Ref. [170] Gyu et al., Sens.
Actuat. B 155 (2011) 366. © Elsevier Publishing).
sensing NO2, it showed a response of ~1.5 for 100 ppm at an
operating temperature of 200 °C. But it responded well with
better selectivity towards H2S. Sputtered coated CuO thin film
with (020) orientation showed a considerable response towards
CO2 gas [162]. The sensing performance of the films which
are sputtered with low and high deposition rate was
investigated. Among these two films, film prepared at lower
deposition rate showed a better response towards CO2 at the
operating temperature of 160 °C. CuO thick film showed a
response towards 30 ppm of SO2 at 200 °C but further increase
in the operating temperature had no influence on the response.
Hollow and hierarchical CuO microspheres detected the
presence of CO gas and C2H5OH vapour at the operating
temperature of 320 °C and 230 °C respectively [163]. The post
annealed microspheres with compact and rough surface
showed a response of ~12 towards 400 ppm of CO gas. CuO
microspheres synthesized by thermal evaporation method
showed a response of ~250 towards 5 ppm of H 2S in the
presence of other gases like Cl2, CO, NH3, NO and CH4 [101].
While the spin coated CuO thin film showed a response to H 2S
at 200 °C. Hence one could understand the role of operating
temperature in tuning the sensor performance and in turn, the
figure of merits. Nanocrystalline CuO powders with 27 nm
crystallite size were used to fabricate thick film ammonia
sensor. Because of the high surface area, maximum porosity
and catalytic activity [164], it exhibited a considerable
response towards ammonia at room temperature. The CuO thin
film deposited using spray pyrolysis technique showed a
response of ~25 towards 10 ppm of ethanol at room
temperature [165]. While the same film which was annealed at
400 °C showed an enhanced response.
3.2.2. Nickel oxide (NiO)
Chemically stable nickel oxide has excellent electrical
properties with the band gap of 4.3 eV. The nearly filled 3d
orbital plays a vital role in using this material for
chemiresistive modulation. Since, the deposition methods and
preparation conditions or parameters strongly influence or
determine the properties of thin film based sensing elements,
NiO thin films were deposited by modulating the various
parameters using reactive magnetron sputtering to detect NO 2
[79] and CO gases [166]. It was found that the material
synthesized with higher oxygen content of 40%, exhibited a
response towards NO2 at 160 °C and CO at 420 °C. But the
NiO surface failed to compete with the discussed metal oxides
(ZnO, SnO2, In2O3, WO3 and CuO) towards the sensing of CO2
and NH3 [167]. The interaction of SO2 molecules with the NiO
surface was investigated by Li and Henrich to understand the
12
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
mechanism where NiO film with different stoichiometric
conditions [168]. Authors have highlighted the influence of
oxygen vacancies in detecting SO2. NiO thin film sensor
synthesized using gas evaporation technique showed a
considerable response towards oxidizing (NO2) and reducing
(H2S) gases [169]. The selectivity of this sensor was
determined by the modulating operating temperature and the
authors observed a response for 10 ppm of NO 2 at 112.5 °C
and H2S at 150 °C. The NiO thin film fabricated employing
colloidal template and sputtering methods exhibited a response
of ~1.5 towards 5 ppm of C2H5OH [170]. While the hollow
hemispherical morphology obtained by annealing the same
samples showed an enhanced response. The enhanced surface
to volume ratio and porosity of the hollow hemispherical
structures (Figure 12) might have promoted the gas solid
interaction and hence the response.
4. Discussion
The atmosphere in wet and dry states acts as a donor
(reducing gas) and acceptor (oxidizing gas) of electrons
respectively from the surface of the metal oxide because of the
presence of water vapour and oxygen. Therefore, the response
of a metal oxide is enhanced or reduced by the atmosphere
towards a particular gas and depends on either the target gas or
type of material surface. Although some authors have reported
better sensing of a particular metal oxide towards a target gas
in wet and dry atmospheres, in general both humidity and
oxygen are present in varying ratios in a typical measuring
ambience. The laboratory studies are normally conducted in
dry atmosphere because the adsorbed oxygen molecules
readily open the binding link for other gases and increases its
sensitivity. Further, higher operating temperatures suppress the
humidity level and many cases enhance the reaction kinetics of
the gas molecules. Recently, a ZnO sensor for ammonia with
high selectivity and immunity to humidity was reported [109]
implying that besides the ambient temperature, material
properties of the metal oxide play an important role in deciding
its sensing properties.
All the gas molecules, have its own bond length, bond
energies, HOMO and LUMO energy levels [171]. For
example, in the case of ethanol, bond energies of H-OC2H5, H-
CH and H-CH2 bonds are 436, 452 and 473 kJ/mol
respectively [130]. The close matching of these bond energies
with respect to the surface energy of the metal oxide play an
important role in the selectivity and strength of adsorption of
gases on metal oxide surface. The possible orientations of
ethanol molecule on the metal oxide surface during interaction
are depicted in the Figure 13. The top three orientations in the
figure correspond to the fore-mentioned three binding
energies. By modifying the operating temperature, the bond
energies can be modified thus changing the favorable
orientation of the gas molecule and hence the strength of
adsorption. The operating temperature can also influence the
semiconducting property of the metal oxides by increasing and
accelerating the carrier charges. It is also possible to switch the
nature of semiconductor between p-type and n-type. An author
reported that at elevated temperature ceria effectively selects
the ethanol rather than tri-methylamine (TMA) whose nature
has been switched from n- to p-type [172].
From the REDOX mechanisms discussed for various
gases, it is clear that the transfer of electrons and number of
Cognizure
www.cognizure.com/pubs
Science Letters Journal Sci. Lett. J. 2015, 4: 126

Figure 13. The possible ways of ethanol molecule interacts on the metal oxide surface.

Table 2. Key parameters to be considered during the synthesis.

Sl. Synthesis method Optimizing Key parameters

1. Sputtering (RF/DC) Source – Substrate distance, Substrate temperature, Anode potential, Ratio of Argon and
other (oxygen) gas, Working pressure, Deposition time, DC: applied voltage and RF:
applied power and impedance matching
2. Spray pyrolysis Substrate temperature, Substrate-Spray nozzle distance, Spray nozzle/gun diameter,
Solution flow rate, Applied gas pressure, Applied frequency (power) – Ultrasonic spray and
Applied flame in the ambient – Flame spray
3. Sol gel Precursor medium, Stabilizing agent, Ratio of solute and stabilizing agent, Ageing
(Processing) time, Drying temperature, Preheating temperature
Dip Coating
Dip / Retrieval speed, Dip duration and Number of Dip
Spin Coating
Substrate rotation speed and Number of cycles
4. Hydrothermal Precursor medium, Surfactant, Processing temperature and duration, Washing method and
Medium, Drying temperature and duration and Sintering temperature and duration
5 Thermal Evaporation Target or Source, Reactive atmosphere, Working pressure, Applied voltage/current,
Substrate and target distance and Annealing temperature

electrons transferred between the metal oxide and target gas
decides the response of the metal oxide. The charge transfer
between the metal oxide and the gases in turn depends on the
number of active sites available on the surface, which depends
on the carrier density and the structural arrangements of the
surface.
The metal oxide materials synthesized by various
methods such as sputtering, thermal evaporation, spray
pyrolysis, sol-gel (dip and spin coating), sonochemical, vapour
phase solution and hydrothermal method produced thin films
with different morphologies like nanoparticles, nanorods,
nanowires, nanoflowers, etc. It can be seen that these materials
have shown entirely different response behaviour towards
various gases. The wide variations in the response and
selectivity behaviour of various metal oxides are due to the
optimization of their respective synthesis parameters in
addition to the operating temperature. Table 2 describes some
key parameters to be considered in various synthesis methods.
The property of the metal oxide depends strongly on the
synthesis method and its preparation conditions [144]. For
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
example, Zhou et al. have reported changes in the sensing
properties of SnO2 metal oxide thin films synthesized by sol-
gel (dip coating) towards detection of H2S gas by varying the
processing (stirring) time of the precursor solution from 1 hr
[140] to 5 hours [141]. This increase in processing time alters
the material behaviour towards sensing. Similarly, the sensing
response can be optimized in the sputtering method by
obtaining different crystal orientations through substrate
temperature. The ZnO thin films with 002 and 100 plane
orientations have been obtained at substrate temperature of 153
°C and 130 °C respectively [119]. The thin film with plane
orientation 100 reportedly has relatively smaller grain size of
20.66 nm and showed better response for CO2 molecules.
Thus, thin film surfaces with certain crystalline orientation and
grain size has better sensing towards a particular gas molecule.
Every crystallographic plane has its own surface state density,
electronic energy levels - donor/acceptor energy making the
chemisorption characteristics. Hence, the response of a metal
oxide film towards a particular gas strongly depends on the
orientation of the crystal surface [58]. Further, morphology of
13
 Science Letters Journal Sci. Lett. J. 2015, 4: 126

Table 3. The material property and sensing parameter of zinc oxide material.

Lattice
Sensing Parameter
Synthesis Parameter Crystallite
Plane Morphology Ref.
method size (nm) Temperature
a (Å) c (Å) Gas Response
(°C)
Wet chemical ~ 10
101 3.24 5.21 18 Nanoflower CO 300 [178]
process (100 ppm)
~ 50
Sol-gel 002 3.25 5.2 15 Nanoparticles NH3 300 [105]
(80 ppm)
~ 37
Spin coating 101 3.265 5.214 73.48 Nanoparticles NO2 200 [123]
(100 ppm)
70-110/0.2- ~ 100
Hydrothermal 101 - - Nanorods H2S 25 [130]
1.3 (10 ppm)
Sputtering 100 - - 20.66 - CO2 100 ~ 2.17 [119]

Table 4. The ethanol sensing response of anion and cation doped – ZnO material.

Electronic Concentration Temperature

Synthesis method Dopants Response Ref.
configuration (ppm) (°C)
Al
Spray Pyrolysis [Ne]3s2 3p1 80 402 160 [23]
(1.8 at. %)
Al
Pulsed layer deposition [Ne]3s2 3p1 200 ~25 ~170 [175]
(wt. 3 %)
In
Spray Pyrolysis [Kr] 4d10 5s2 5p1 80 402 ~72 [23]
(6.5 at. %)
Sn
Dip [Kr] 4d10 5s2 5p2 300 300 ~58 [179]
(4at. %)
Mn
Spray Pyrolysis [Ar] 3d5 4s2 50 100 ~18 [180]
(4 at. %)
Fe
Spray Pyrolysis [Ar] 3d6 4s2 80 402 ~100 [23]
(1.1 at. %)
Hydrothermal method and Co
[Ar] 3d7 4s2 50 350 ~10.9 [181]
electrochemical process (1.8 %)
Cu
Spray Pyrolysis [Ar] 3d104s1 80 402 ~30 [23]
(3.6 at. %)

the metal oxide affects the response as it changes the number
of active sites for adsorption. Among, the ZnO based metal
oxide sensors with nanorod [134], nanowire [132], nanoflower
[104], nanotube [131] and granular nanoparticle [173]
morphologies reported, granular nanoparticles were found to
have better response to ethanol. The grain size, which can be
controlled by the synthesis parameters play a major role in
determining the sensing properties [174]. The sensitivity was
highly enhanced because of the grain size reduction [20] and it
is one of the most important factors of the metal oxides since it
controls all the operating characteristics of the gas sensor
[174]. For better understanding, let us consider ZnO as an
example to have an insight on the influence of synthesis
method on its structural and sensing properties. Table 3
provides a list of ZnO films produced by different synthesis
methods along with their structural and sensing parameters. It
can be seen that sensing property depends on all the structural
properties listed and varying sensing characteristics can be
expected by choosing different synthesis method.
The lattice parameters of ZnO thin films listed in
Table 3, corresponds to hexagonal wurtzite structure.
However, since different synthesis method is chosen, they
showed response to different gases and operating temperature
as they have different grain sizes, crystal orientations and
morphology. The difference in the grain size, crystal
orientation and morphology modifies the nature of the active
sites for the adsorption of gas molecules. The direct
dependence of carrier density on the grain or crystallite size,
surface morphology and crystal orientation explains the
14
© Cognizure. All rights reserved.
varying selectivity and sensing properties of thin films
produced by different synthesis techniques.
Density functional study reveals that the electrical
properties and hence the sensing properties of zinc oxide
depends on its geometrical structure [70]. Spencer [70] have
extended the study to show that the dopants can alter the
electronic properties of the material and enhance the sensing
response. The dopants can enhance the sensing characteristics
of the metal oxide surfaces by lowering the energy required for
chemisorption of gas molecules. The precise choice of the type
of dopant and optimizing its concentration is required for
getting better sensing performance [23]. The dopants in the
metal oxide semiconductors can be broadly classified as
n-type/anion (metal atoms such as Aluminium (Al), Gallium
(Ga), Indium (In) and Tin (Sn)) and p-type/cation (transition
metal atoms such as Manganese (Mn), Iron (Fe), Cobalt (Co),
and Copper (Cu)). Table 4 summarizes the sensing response of
ethanol for the selective dopants in the zinc oxide thin film. It
can be seen that, ZnO with n-type dopant (Al) responded well
at room temperature [175] as well as at elevated temperatures
[23]. Zhou et al. [176] have reported that compared to Li and
3d transition metal (Mn, Co and Cu) doping in ZnO, Al has
better electrical conductivity. The impurity Al in ZnO
increased the conductance by decreasing the grain and grain
boundary resistance than undoped ZnO. In contrast, Cu in ZnO
increased the grain and grain boundary resistance. Obviously,
it shows grain and grain boundary resistance can control and
enhance the transduction and receptor function of the metal
oxide gas sensor. Therefore, by doping with appropriate choice
Cognizure
www.cognizure.com/pubs
Science Letters Journal Sci. Lett. J. 2015, 4: 126

of the type and concentration of dopant material in metal Acknowledgements

oxide, the sensing properties can be enhanced by controlling
the grain size and grain boundary resistance. Further, doping
highly electronegative elements like fluorine has influenced
the sensing characteristics by the phenomena of grain
boundary scattering. As the consequence of this, the trend in
change in resistance while interacting with gas is reversed,
which, in turn, can be used to enhance the selectivity of the
sensing element [177].
The authors wish to express their sincere thanks to the
Department of Science & Technology, New Delhi, India for
their financial support (INT/SWD/VINN/P-04/2011). They
also wish to acknowledge SASTRA University, Thanjavur for
extending infrastructural support to carry out this work. We
would like to thank Dr. Gopinath Mudhana, Asst. Prof., for his
valuable suggestions.

5. Conclusions References

Although, metal oxide films produced by various 1.
synthesis methods demonstrate different sensing properties,
regardless of the synthesis method, the following implicit and 2.
explicit practical considerations with reference to material
3.
preparation and the film growth must be considered to 4.
determine the response of a specific material towards a
specific gas. The most dominant feature of the sensing element 5.
namely “grain size”, which influences the individual grain
resistance as well as the grain boundary resistance at the 6.
material surface must be tailor made by exactly controlling the
nucleation and growth processes. This can be achieved not 7.
only by optimizing the synthesis parameters but also by 8.
introducing specific dopants with modulated concentrations.
While selecting the dopants, the type of the semiconducting 9.
host material, the electron affinity of the dopants 10.
(cation/anion), its ionic radii, and the possibility of orbital 11.
hybridisation may be considered to fine tune the grain size for 12.
better sensing and transduction functions. For further
enhancement of the sensing properties, the grain size has to be 13.
made comparable to the extent of space charge region. The 14.
correct choice of the type of dopant and its concentration helps
in engineering the carrier concentration, desired density of 15.
states and hence the band gap, which increases the surface 16.
catalytic activity aiding the enhancement of the adsorption of
the desired gas at the surface. The enhancement of surface 17.
adsorption not only increases the response of the sensing
element but also significantly reduces the operating 18.
temperature almost to the room temperature. The room 19.
temperature gas sensor can also be realized through quantum
confinement processes. The effect of humidity, which is a 20.
major hindrance for the metal oxide based gas sensors can be 21.
reduced to less than 2% by making electronic conductivity 22.
more dominant than ionic by careful engineering of the grain
boundary resistance. In principle any metal oxide discussed
can sense a given gas molecule. However, refining their 23.
surface properties to match the LUMO level of the gas of
interest with the surface energy of the selected sensing 24.
material is required to effectively sense a particular gas
molecule. 25.
The possibility of changing the nature of sensing
26.
materials from n- to p-type or p- to n-type conductivity during
the gas solid interaction has to be explored to minimize or 27.
even eliminate the most challenging issue of selectivity.
Further, the grain boundary scattering in the nano scale 28.
materials during gas solid interaction and its relation to the
film thickness need to be explored as another option for 29.
enhancing the selectivity.
30.
31.
V.-M. Guérin, J. Rathousky, T. Pauporté, Sol. Energy Mater.
Sol. Cells 102 (2012) 8.
H.-J. Park, K.-H. Lee, B. Kumar, K.-S. Shin, S.-W. Jeong, S.-W.
Kim, J. Nanoelectron. Optoelectron. 5 (2010) 135.
C. Klingshirn, Phys. Status Solidi 244 (2007) 3027.
M. Godlewski, E. Guziewicz, K. Kopalko, G. Łuka, M. I.
Łukasiewicz, Low Temp. Phys. 37 (2011) 235.
R. Chakraborty, U. Das, D. Mohanta, A. Choudhury, Indian J.
Phys. 83 (2009) 553.
R. Saravanan, K. Santhi, N. Sivakumar, V. Narayanan, A.
Stephen, Mater. Charact. 67 (2012) 10.
Z. L. Wang, Appl. Phys. A 88 (2007) 7.
E. Comini, G. Faglia, G. Sberveglieri, In: E. Comini, G. Faglia,
G. Sberveglieri (Eds.), Solid State Gas Sensors, Springer (2009)
p. 47–107.
C. G. B. Garrett, W. H. Brattain, Phys. Rev. 99 (1955) 376.
W. H. Brattain, C. G. B. Garrett, Physica 20 (1954) 885.
W. H. Brattain, J. Bardeen, Bell Labs Tech. J. 32 (1953) 1.
T. Seiyama, A. Kato, K. Fujiishi, M. Nagatani, Anal. Chem. 34
(1962) 1502.
T. Seiyama, S. Kagawa, Anal. Chem. 38 (1966) 1069.
N. Taguchi, Gas Detecting Device, US Patent 3, 695, 848
(1972).
N. Yamazoe, G. Sakai, K. Shimanoe, Catal. Surv. Asia 7 (2003)
63.
N. Yamazoe, Y. Kurokawa, T. Seiyama, Sensor. Actuator. 4
(1983) 283.
P. Tyagi, A. Sharma, M. Tomar, V. Gupta, Chem. Sensors 4
(2014) 18.
A. Sharma, M. Tomar, V. Gupta, J. Nanosci. Lett. 2 (2014) 27.
C. Xu, J. Tamaki, N. Miura, N. Yamazoe, Sens. Actuat. B 3
(1991) 147.
N. Yamazoe, Sens. Actuat. B 5 (1991) 7.
Z. Bai, C. Xie, M. Hu, S. Zhang, D. Zeng, Mater. Sci. Eng. B
149 (2008) 12.
K. Wetchakun, T. Samerjai, N. Tamaekong, C. Liewhiran, C.
Siriwong, V. Kruefu, A. Wisitsoraat, A. Tuantranont, S.
Phanichphant, Sens. Actuat. B 160 (2011) 580.
F. Paraguay, M. Miki-Yoshida, J. Morales, J. Solis, W. E. L.,
Thin Solid Films 373 (2000) 137.
A. Fort, M. Mugnaini, S. Rocchi, V. Vignoli, E. Comini, G.
Faglia, A. Ponzoni, Sens. Actuat. B 148 (2010) 283.
J. D. D. Prades, A. Cirera, J. R. R. Morante, Sens. Actuat. B 142
(2009) 179.
J. Guérin, K. Aguir, M. Bendahan, Sens. Actuat. B 119 (2006)
327.
J. J. J. Velasco-Velez, C. Wilbertz, T. Haas, T. Doll, Procedia
Chem. 1 (2009) 642.
V. E. Bochenkov, G. B. Sergeev, Adv. Colloid Interface Sci. 116
(2005) 245.
M. M. Arafat, B. Dinan, S. A. Akbar, A. S. M. A. Haseeb,
Sensors 12 (2012) 7207.
R. Boppella, P. Manjula, S. Arunkumar, S. V Manorama, Chem.
Sensors 4 (2014) 19.
G. F. Fine, L. M. Cavanagh, A. Afonja, R. Binions, Sensors 10
(2010) 5469.

Cognizure 15
www.cognizure.com/pubs © Cognizure. All rights reserved.
 Science Letters Journal
32. X. Wang, S. S. Yee, W. P. Carey, Sens. Actuat. B 24-25 (1995)
454.
33. T. Seyama, H. Futata, F. Era, N. Yamazoe, Denki Kagaku 40
(1972) 244.
34. S. Xu, Z. L. Wang, Nano Res. 4 (2011) 1013.
35. S. Kannan, L. Rieth, F. Solzbacher, Sens. Actuat. B 149 (2010)
8.
36. G. Korotcenkov, Sens. Actuat. B 107 (2005) 209.
37. E. Comini, C. Baratto, G. Faglia, M. Ferroni, A. Vomiero, G.
Sberveglieri, Prog. Mater Sci. 54 (2009) 1.
38. S. Barth, F. Hernandez-Ramirez, J. D. Holmes, A. Romano-
Rodriguez, Prog. Mater Sci. 55 (2010) 563.
39. J. G. Lu, P. Chang, Z. Fan, Mater. Sci. Eng. R 52 (2006) 49.
40. F. Fang, J. Futter, J. Kennedy, A. Markwitz, 2011 Fifth Int.
Conf. Sens. Technol. (2011) p. .
41. J. L. Gomez, O. Tigli, J. Mater. Sci. 48 (2012) 612.
42. Z. Zhang, M. G. Lagally, Science 276 (1997) 377.
43. T. Hübert, L. Boon-brett, G. Black, U. Banach, Sens. Actuat. B
157 (2011) 329.
44. N. Yamazoe, K. Shimanoe, Sens. Actuat. B 138 (2009) 100.
45. G. Heiland, Sensor. Actuator. 2 (1982) 343.
46. N. Yamazoe, Sens. Actuat. B 108 (2005) 2.
47. C. Wang, L. Yin, L. Zhang, D. Xiang, R. Gao, Sensors 10 (2010)
2088.
48. Y. Shimizu, M. Egashira, MRS Bull. 24 (1999) 18.
49. N. Barsan, D. Koziej, U. Weimar, Sens. Actuat. B 121 (2007)
18.
50. D. Kohl, J. Phys. D Appl. Phys. 34 (2001) R125.
51. S. Basu, P. K. Basu, Sens. Transducers J. 134 (2011) 1.
52. N. Yamazoe, K. Shimanoe, Sens. Actuat. B 160 (2011) 1352.
53. W. Göpel, Prog. Surf. Sci. 20 (1985) 9.
54. C. Engler, W. Lorenz, Surf. Sci. 104 (1981) 549.
55. N. Yamazoe, K. Shimanoe, J. Sens. 2009 (2009) 875704.
56. G. Korotcenkov, V. Brinzari, J. R. Stetter, I. Blinov, V. Blaja,
Sens. Actuat. B 128 (2007) 51.
57. N. Barsan, U. Weimar, J. Electroceram. 7 (2001) 143.
58. G. Korotcenkov, Mater. Sci. Eng. R 61 (2008) 1.
59. G. Jiménez-Cadena, J. Riu, F. X. Rius, G. Jime, Analyst 132
(2007) 1083.
60. X.-J. Huang, Y.-K. Choi, Sens. Actuat. B 122 (2007) 659.
61. J. Huang, Q. Wan, Sensors 9 (2009) 9903.
62. E. Comini, Anal. Chim. Acta 568 (2006) 28.
63. E. Comini, G. Sberveglieri, Mater. Today 13 (2010) 36.
64. T. Asefa, C. T. Duncan, K. K. Sharma, Analyst 134 (2009) 1980.
65. O. K. Varghese, C. A. Grimes, J. Nanosci. Nanotechnol. 3
(2003) 277.
66. K. R. Nemade, Sens. Transducers J. 132 (2011) 1.
67. S. M. Kanan, O. M. El-Kadri, I. A. Abu-Yousef, M. C. Kanan,
Sensors 9 (2009) 8158.
68. D. E. Williams, Sens. Actuat. B 57 (1999) 1.
69. V. M. Aroutiounian, G. S. Aghababian, Sens. Actuat. B 50
(1998) 80.
70. M. J. S. S. Spencer, Prog. Mater Sci. 57 (2012) 437.
71. D. H. Kim, J. Y. Yoon, H. C. Park, K. H. Kim, Sens. Actuat. B
62 (2000) 61.
72. O. Wurzinger, G. Reinhardt, Sens. Actuat. B 103 (2004) 104.
73. G. Heiland, D. Kohl, In: T. Seiyama (Ed.), Chemical Sensors
Technology, Elsevier, Amsterdam (1988) p. 15–38.
74. N. Barsan, M. Schweizer-Berberich, W. Göpel, Fresenius J.
Anal. Chem. 365 (1999) 287.
75. P. K. Kannan, R. Saraswathi, J. B. B. Rayappan, Sens. Actuat. A
164 (2010) 8.
76. S. R. Morrison, The Chemical Physics of Surfaces, Springer,
New York (1990).
77. V. E. Henrich, P. A. Cox, The Surface Science of Metal Oxides,
Cambridge University Press, New York (1994).
78. S. Capone, P. Siciliano, Encycl. Nanosci. Nanotechnol. 3 (2004)
769.
79. I. Hotovy, V. Rehacek, P. Siciliano, S. Capone, L. Spiess, Thin
Solid Films 418 (2002) 9.
16
© Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
80. N. D. Hoa, S. Y. An, N. Q. Dung, N. Van Quy, D. Kim, N. Van
Quy, Sens. Actuat. B 146 (2010) 239.
81. S. R. Morrison, Sens. Actuat. B 11 (1987) 283.
82. O. K. Varghese, C. A. Grimes, Encycl. Nanosci. Nanotechnol. 5
(2004) 505.
83. B. Ostrick, M. Fleischer, H. Meixner, C.-D. Kohl, Sens. Actuat.
B 68 (2000) 197.
84. M. J. Madou, S. R. Morrison, Chemical Sensing with Solid State
Devices, Academic Press, San Diego (1989).
85. T. Krishnakumar, R. Jayaprakash, T. Prakash, D. Sathyaraj, N.
Donato, S. Licoccia, M. Latino, A. Stassi, G. Neri,
Nanotechnology 22 (2011) 325501.
86. S. L. Bai, J. W. Hu, R. X. Luo, D. Q. Li, A. F. Chen, C. C. Liu,
X. Xu, IEEE Sens. J. 12 (2012) 1234.
87. M. B. Rahmani, S. H. Keshmiri, M. Shafiei, K. Latham, W.
Wlodarski, J. du Plessis, K. Kalantar-Zadeh, Sens. Lett. 7 (2009)
1.
88. S. Kannan, H. Steinebach, L. Rieth, F. Solzbacher, Sens. Actuat.
B 148 (2010) 126.
89. A. Gurlo, N. Barsan, M. Ivanovskaya, U. Weimar, W. Göpel,
Sens. Actuat. B 47 (1998) 92.
90. H. Xia, Y. Wang, F. Kong, S. Wang, B. Zhu, X. Guo, J. Zhang,
S. Wu, Sens. Actuat. B 134 (2008) 133.
91. A. Sharma, M. Tomar, V. Gupta, Sens. Actuat. B 156 (2011)
743.
92. J. A. Rodriguez, T. Jirsak, S. Chaturvedi, M. Kuhn, A.
Rodriguez, Surf. Sci. 442 (1999) 400.
93. C. M. Kim, Bull. Korean Chem. Soc. 27 (2006) 2037.
94. M. Hübner, C. E. E. Simion, S. Pokhrel, N. Bârsan, U. Weimar,
A. Tomescu-Stănoiu, Sens. Actuat. B 153 (2011) 347.
95. M. Hübner, C. E. Simion, A. Haensch, N. Barsan, U. Weimar,
Sens. Actuat. B 151 (2010) 103.
96. B. M. Matin, Y. Mortazavi, A. A. Khodadadi, A. Abbasi, A. A.
Firooz, B. Mehrabi Matin, A. Anaraki Firooz, Sens. Actuat. B
151 (2010) 140.
97. J. Xu, X. Wang, J. Shen, Sens. Actuat. B 115 (2006) 642.
98. R. Kumar, A. Khanna, V. S. Sastry, Vacuum 86 (2012) 1380.
99. T. W. Capehart, S. C. Chang, J. Vac. Sci. Technol. 18 (1981)
393.
100. T. Pagnier, M. Boulova, A. Galerie, A. Gaskov, G. Lucazeau, J.
Solid State Chem. 143 (1999) 86.
101. N. S. Ramgir, S. K. Ganapathi, M. Kaur, N. Datta, K. P. Muthe,
D. K. Aswal, S. K. Gupta, J. V. Yakhmi, Sens. Actuat. B 151
(2010) 90.
102. C. S. Rout, M. Hegde, C. N. R. Rao, Sens. Actuat. B 128 (2008)
488.
103. T. Nguyen, S. Park, J. B. Kim, T. K. Kim, G. H. Seong, J. Choo,
Y. S. Kim, J. Beom, T. Kyu, G. Hun, Y. Shin, Sens. Actuat. B
160 (2011) 549.
104. N. K. Singh, S. Shrivastava, S. Rath, S. Annapoorni, Appl. Surf.
Sci. 257 (2010) 1544.
105. C. S. Rout, M. Hegde, A. Govindaraj, C. N. R. Rao,
Nanotechnology 18 (2007) 205504.
106. J. B. K. Law, J. T. L. Thong, Nanotechnology 19 (2008) 205502.
107. A. Wei, Z. Wang, L.-H. Pan, W.-W. Li, L. Xiong, X.-C. Dong,
W. Huang, Chin. Phys. Lett. 28 (2011) 080702.
108. M. Stankova, X. Vilanova, E. Llobet, J. Calderer, C. Bittencourt,
J. J. Pireaux, X. Correig, Sens. Actuat. B 105 (2005) 271.
109. G. K. Mani, J. B. B. Rayappan, Sens. Actuat. B 183 (2013) 459.
110. D. Chen, X. Hou, H. Wen, Y. Wang, H. Wang, X. Li, R. Zhang,
H. Lu, H. Xu, S. Guan, J. Sun, L. Gao, Nanotechnology 21
(2010) 035501.
111. F. Hellegouarc‟h, F. Arefi-Khonsari, R. Planade, J. Amouroux,
Sens. Actuat. B 73 (2001) 27.
112. R. S. Khadayate, R. B. Waghulde, M. G. Wankhede, J. V Sali, P.
P. Patil, Bull. Mater. Sci. 30 (2007) 129.
113. P. P. Sahay, S. Tewari, S. Jha, M. Shamsuddin, J. Mater. Sci. 40
(2005) 4791.
114. L. A. Patil, M. D. Shinde, A. R. Bari, V. V. Deo, Curr. Appl
Phys. 10 (2010) 1249.
Cognizure
www.cognizure.com/pubs
Science Letters Journal
115. R. C. Singh, O. Singh, M. P. Singh, P. S. Chandi, R. Chand, M.
Pal, P. Singh, Sens. Actuat. B 135 (2008) 352.
116. E. Comini, G. Faglia, G. Sberveglieri, D. Calestani, L. Zanotti,
M. Zha, Sens. Actuat. B 111-112 (2005) 2.
117. J. Xu, J. Han, Y. Zhang, Y. Sun, B. Xie, Sens. Actuat. B 132
(2008) 334.
118. L. Schmidt-mende, J. L. Macmanus-driscoll, Mater. Today 10
(2007) 40.
119. P. Samarasekara, N. U. S. Yapa, N. T. R. N. Kumara, M. V. K.
Perera, Bull. Mater. Sci. 30 (2007) 113.
120. L. Shi, A. J. T. Naik, J. B. M. Goodall, C. Tighe, R. Gruar, R.
Binions, I. Parkin, J. Darr, Langmuir 29 (2013) 10603.
121. L. Liao, H. B. Lu, J. C. Li, H. He, D. F. Wang, D. J. Fu, C. Liu,
W. F. Zhang, J. Phys. Chem. C 111 (2007) 1900.
122. J. Y. Park, S.-W. Choi, S. S. Kim, Nanoscale Res. Lett. 5 (2010)
353.
123. M. A. Chougule, S. Sen, V. B. Patil, Ceram. Int. 38 (2012) 2685.
124. N. Tamaekong, C. Liewhiran, A. Wisitsoraat, S. Phanichphant,
Sensors 10 (2010) 7863.
125. P.-S. Cho, K.-W. Kim, J.-H. Lee, J. Electroceram. 17 (2006)
975.
126. Y. Zeng, L. Qiao, Y. Bing, M. Wen, B. Zou, W. Zheng, T.
Zhang, G. Zou, Sens. Actuat. B 173 (2012) 897.
127. V. A. T. Dam, M. A. Blauw, S. H. Brongersma, M. Crego-
Calama, Procedia Eng. 5 (2010) 172.
128. G. K. Mani, J. B. B. Rayappan, J. Alloys Compd. 582 (2014)
414.
129. S. K. Gupta, A. Joshi, M. Kaur, J. Chem. Sci. 122 (2010) 57.
130. C. Wang, X. Chu, M. Wu, Sens. Actuat. B 113 (2006) 320.
131. Y.-J. Chen, C.-L. Zhu, G. Xiao, Sens. Actuat. B 129 (2008) 639.
132. Q. Wan, Q. H. Li, Y. J. Chen, T. H. Wang, X. L. He, J. P. Li, C.
L. Lin, Appl. Phys. Lett. 84 (2004) 3654.
133. W. Guo, T. Liu, H. Zhang, R. Sun, Y. Chen, W. Zeng, Z. Wang,
Sens. Actuat. B 166-167 (2012) 492.
134. L. Wang, Y. Kang, X. Liu, S. Zhang, W. Huang, S. Wang, Sens.
Actuat. B 162 (2012) 237.
135. X. Zhou, Q. Xue, H. Chen, C. Liu, Physica E 42 (2010) 2021.
136. H. J. Pandya, S. Chandra, A. L. Vyas, Sens. Actuat. B 161
(2012) 923.
137. P. Shankar, J. B. B. Rayappan, Sens. Lett. 11 (2013) 1956.
138. C. M. Ghimbeu, M. Lumbreras, M. Siadat, R. C. van
Landschoot, J. Schoonman, R. C. van Landschoot, Sens. Actuat.
B 133 (2008) 694.
139. S. A. Waghuley, Indian J. Pure Appl. Phys. 49 (2011) 816.
140. G. Shuping, X. Jing, L. L. Jianqiao, Z. Dongxiang, Sens. Actuat.
B 134 (2008) 57.
141. J. Liu, S. Gong, J. Xia, L. Quan, H. Liu, D. Zhou, Sens. Actuat.
B 138 (2009) 289.
142. X. Du, S. M. George, Sens. Actuat. B 135 (2008) 152.
143. L. Xi, D. Qian, X. Tang, C. Chen, Mater. Chem. Phys. 108
(2008) 232.
144. A. Gurlo, M. Ivanovskaya, N. Barsan, M. Schweizer-Berberich,
U. Weimar, W. Göpel, A. Dieguez, Sens. Actuat. B 44 (1997)
327.
145. H. Steffes, C. Imawan, F. Solzbacher, E. Obermeier, Sens.
Actuat. B 78 (2001) 106.
146. S. K. Lim, S. Hwang, D. Chang, S. Kim, Sens. Actuat. B 149
(2010) 28.
147. S. C. Kulkarni, R. Y. Borse, Sens. Transducers J. 125 (2011)
194.
148. P. Feng, X. Y. Xue, Y. G. Liu, T. H. Wang, Appl. Phys. Lett. 89
(2006) 243514.
149. G. Sberveglieri, L. Depero, S. Groppelli, P. Nelli, Sens. Actuat.
B 26-27 (1995) 89.
150. Y. Shen, T. Yamazaki, Z. Liu, D. Meng, T. Kikuta, N. Nakatani,
Thin Solid Films 517 (2009) 2069.
151. E. K. Heidari, C. Zamani, E. Marzbanrad, B. Raissi, S.
Nazarpour, Sens. Actuat. B 146 (2010) 165.
152. A. Ponzoni, E. Comini, M. Ferroni, G. Sberveglieri, Thin Solid
Films 490 (2005) 81.
Cognizure
www.cognizure.com/pubs © Cognizure. All rights reserved.
Sci. Lett. J. 2015, 4: 126
153. J. Leng, X. Xu, N. Lv, H. Fan, T. Zhang, J. Colloid Interface Sci.
356 (2011) 54.
154. C. M. Ghimbeu, M. Lumbreras, J. Schoonman, M. Siadat,
Sensors 9 (2009) 9122.
155. X. Chang, S. Sun, Y. Yin, Mater. Chem. Phys. 126 (2011) 717.
156. E. Llobet, G. Molas, P. Molinàs, J. Calderer, X. Vilanova, J.
Brezmes, J. E. Sueiras, X. Correig, J. Electrochem. Soc. 147
(2000) 776.
157. S. Park, H. Kim, C. Jin, S.-W. Choi, S. S. Kim, C. Lee,
Thermochim. Acta 542 (2012) 69.
158. J. L. Solis, S. Saukko, L. B. Kish, C. G. Granqvist, V. Lantto,
Sens. Actuat. B 77 (2001) 316.
159. T. Vogt, P. M. Woodward, B. A. Hunter, J. Solid State Chem.
144 (1999) 209.
160. J. Pike, S. Chan, F. Zhang, X. Wang, J. Hanson, Appl. Catal. A
303 (2006) 273.
161. D. Jundale, S. Pawar, M. Chougule, P. Godse, S. Patil, B. Raut,
S. Sen, V. Patil, J. Sens. Technol. 1 (2011) 36.
162. P. Samarasekara, N. T. R. N. Kumara, N. U. S. Yapa, J. Phys.
Condens. Matter 18 (2006) 2417.
163. Y. Zhang, X. He, J. Li, H. Zhang, X. Gao, Sens. Actuat. B 128
(2007) 293.
164. I. Singh, R. K. Bedi, J. Mater. Sci. 46 (2011) 5568.
165. D. Gopalakrishna, K. Vijayalakshmi, C. Ravidhas, Ceram. Int.
39 (2013) 7685.
166. I. Hotovy, J. Huran, P. Siciliano, S. Capone, L. Spiess, V.
Rehacek, Sens. Actuat. B 78 (2001) 126.
167. H. Steinebach, S. Kannan, L. Rieth, F. Solzbacher, Sens. Actuat.
B 151 (2010) 162.
168. X. Li, V. E. Henrich, Phys. Rev. B 48 (1993) 17486.
169. C. Luyo, R. Ionescu, L. F. F. Reyes, Z. Topalian, W. Estrada, E.
Llobet, C. G. G. Granqvist, P. Heszler, Sens. Actuat. B 138
(2009) 14.
170. N. Gyu, I.-S. Hwang, H. Kim, J. Lee, I.-D. Kim, N. G. Cho,
Sens. Actuat. B 155 (2011) 366.
171. Z. Wen, L. Tian-mo, Physica B 405 (2010) 1345.
172. K. L. A. Kumar, S. Durgajanani, B. G. Jeyaprakash, J. B. B.
Rayappan, K. Lokaiah, A. Kumar, J. Bosco, B. Rayappan, Sens.
Actuat. B 177 (2013) 19.
173. Y. Zhang, X. Zheng, X. Zhong, S. Deng, Meas. Sci. Technol. 23
(2012) 105107.
174. G. Korotcenkov, S.-D. Han, B. K. Cho, V. Brinzari, Crit. Rev.
Solid State Mater. Sci. 34 (2009) 1.
175. D. Y. Kim, J. Y. Son, Electrochem. Solid-State Lett. 12 (2009)
J109.
176. Z. Zhou, K. Kato, T. Komaki, M. Yoshino, H. Yukawa, M.
Morinaga, K. Morita, J. Eur. Ceram. Soc. 24 (2004) 139.
177. D. Sivalingam, J. B. B. Rayappan, S. Gandhi, S.
Madanagurusamy, R. K. Sekar, U. M. Krishnan, Int. J. Nanosci.
10 (2011) 1161.
178. T. Krishnakumar, R. Jayaprakash, N. Pinna, N. Donato, A.
Bonavita, G. Micali, G. Neri, Sens. Actuat. B 143 (2009) 198.
179. T. Thuy, N. Han, H. Hoang, K. Yul, K. Binh, K. Pillai, J. Yi, T.
T. Trinh, N. H. Tu, H. H. Le, K. Y. Ryu, K. B. Le, Sens. Actuat.
B 152 (2011) 73.
180. D. Sivalingam, J. B. Gopalakrishnan, J. B. B. Rayappan, Sens.
Actuat. B 166-167 (2012) 624.
181. Y. Li, K.-M. Li, C. Wang, C.-I. Kuo, L.-J. Chen, Sens. Actuat. B
161 (2012) 734.
Biographies
Prabakaran Shankar received his M.Sc. degree in Physics
from Bharathidasan University, Tiruchirapalli, India in 2010.
He is pursuing his Ph.D degree in SASTRA University,
Thanjavur, India, from 2011 to date. He is carrying out his
research work in the development of nanomaterials for gas
sensors.
17
 Science Letters Journal Sci. Lett. J. 2015, 4: 126

John Bosco Balaguru Rayappan received his M.Sc. and

Ph.D. degrees in Physics from Bharathidasan University,
Tiruchirapalli, India, in 1996 and 2003 respectively. He is
currently working as a Professor in the School of Electrical &
Electronics Engineering and Centre for Nanotechnology &
Advanced Biomaterials (CeNTAB), SASTRA University,
Thanjavur, India. His current research interests include lattice
dynamics, fabrication of thin film based chemical & biosensors
and functional nanomaterials. He is also working in the field of
embedded systems and steganography.

Cite this article as:

Prabakaran Shankar et al.: Gas sensing mechanism of metal oxides: The role of ambient atmosphere, type of semiconductor
and gases - A review. Sci. Lett. J. 2015, 4: 126

18 Cognizure
© Cognizure. All rights reserved. www.cognizure.com/pubs

View publication stats