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Review
Metal oxides for solid-state gas sensors: What determines our choice?
G. Korotcenkov
Department of Micro- and Optoelectronics, Technical University of Moldova, Chisinau, Republic of Moldova
Received 4 October 2006; received in revised form 15 December 2006; accepted 29 January 2007
Abstract
The analysis of various parameters of metal oxides and the search of criteria, which could be used during material selection for solid-state gas sensor
applications, were the main objectives of this review. For these purposes the correlation between electro-physical (band gap, electroconductivity,
type of conductivity, oxygen diffusion), thermodynamic, surface, electronic, structural properties, catalytic activity and gas-sensing characteristics
of metal oxides designed for solid-state sensors was established. It has been discussed the role of metal oxide manufacturability, chemical activity,
and parameters stability in sensing material choice as well.
2007 Elsevier B.V. All rights reserved.
Keywords: Gas sensors; Metal oxides; Desired properties
1. Introduction
Numerous researches have shown that a characteristic of
solid-state gas sensors is the reversible interaction of the gas
with the surface of a solid-state material [14]. In addition to
the conductivity change of gas-sensing material, the detection
of this reaction can be performed by measuring the change
of capacitance, work function, mass, optical characteristics or
reaction energy released by the gas/solid interaction [516]. Various materials, synthesized in the form of porous ceramics, and
deposited in the form of thick or thin films, are used as active
layers in such gas-sensing devices [1721]. The read-out of the
measured value is performed via electrodes, diode arrangements,
transistors, surface wave components, thickness-mode transducers or optical arrangements. However, in spite of so big variety
of approaches to solid-state gas sensor design the basic operation principles of all gas sensors above mentioned are similar
for all the devices. As a rule, chemical processes, which detect
the gas by means of selective chemical reaction with a reagent,
mainly utilize solid-state chemical detection principles [2,22].
Theoretically there are no limitations for using any materials
for solid-state gas sensors design independently of their physical, chemical, structural or electrical properties. Thousands of
results have been reported about the characteristics and per-
0921-5107/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2007.01.044
Table 1
Comparison of various types of gas sensors
Parameter
Sensitivity
Accuracy
Selectivity
Response time
Stability
Durability
Maintenance
Cost
Suitability to portable instruments
Catalytic combustion
Electro-chemical
Thermal conductive
Infrared absorption
e
g
p
e
g
g
e
e
e
g
g
b
g
g
g
e
e
g
g
g
g
p
b
p
g
g
p
b
g
b
g
g
g
g
g
g
e
e
e
p
g
e
p
p
b
and rate of response) and reliability-related ones (e.g., drift, stability and interfering gases). These are all connected with the
sensing materials used so that the selection and processing of
the sensing materials (materials design) have key importance in
research and development of gas sensors.
Of course this paper cannot include exhaustive reviews of all
available solid-state gas sensors and materials aimed for application in these devices. At present there are three main types of
solid-state gas sensor currently in large-scale use [46]. They
are based on solid electrolytes (electrochemical sensors), on
catalytic combustion (pellistors) and on resistance modulation
of semiconducting oxides (conductometric or chemiresistancebased gas sensors). In this paper the main attention will be
focused on the third type of solid-state sensors. The comparison
of semiconductor gas sensors with another types of solid-state
gas sensors is presented in Table 1.
The semiconductor gas sensors offer low cost, high sensitivity and a real simplicity in function; advantages that should work
in their favor as new applications emerge. Moreover, the possibility of easily combining in the same device the functions of
a sensitive element and signal converter and control electronics
markedly simplifies the design of a sensor and constitutes the
main advantage of chemiresistive-type sensors over biochemical, optical, acoustic, and other gas-sensing devices [22]. A
sensing element of these sensors normally comprising a semiconducting material presenting a high surface-to-bulk ratio is
deployed on a heated insulating substrate between two metallic electrodes. Reactions involving gas molecules can take place
at the semiconductor surface to change the density of charge
carriers available.
It is necessary to note that in spite of the simple working
principle of chemiresistive gas sensor, the gas-sensing mechanism involved is fairly complex. The gas/semiconductor surface
interactions on which is based the gas-sensing mechanism of
chemiresistive gas sensors occur at the grain boundaries of
the polycrystalline oxide film. They generally include reduction/oxidation processes of the semiconductor, adsorption of
the chemical species directly on the semiconductor and/or
adsorption by reaction with surface states associated with preadsorbed ambient oxygen, electronic transfer of delocalized
conduction-band electrons to localized surface states and vice
versa, catalytic effects and in general complex surface chemi-
Fig. 1. Diagram illustrating processes taking place in metal oxides during gas detection and their consequences for polycrystalline metal oxides properties.
and gas response mechanism of sensors on their base, a comparative analysis for indicated materials could be conducted
just for limited number of parameters, controlling gas-sensing
effects.
2. Sensing material choice through their surface
properties
It is known that operating characteristics of solid-state gas
sensors, especially sensitivity, are controlled by three independent factors such as receptor (recognition) function, transducer
function and peculiarities of sensor construction. Receptor function provides the ability of the oxide surface to interact with
the target gas, and transducer function provides the ability to
convert the signal caused by chemical interaction of the oxide
surface into electrical signal [44]. Surface of metal oxides
is responsible for receptor function of solid-state gas sensors [3,4,40,41,55,56,61,62], and therefore this section will be
devoted to brief overview of some surface properties of metal
oxides important for gas sensor operation.
2.1. Density of surface states
The density of native surface states is metal oxide surface
parameter, which has special importance for solid-state gas
sensors. If we want to achieve effective operation of solid-state
gas sensors, the concentration of those states should be
minimized. Only in this case the surface Fermi level will not
be pinned. Indicated surfaces property creates a condition
for modulation of surface potential of semiconductor at the
change of surrounding atmosphere, because the charge of native
(1)
(2)
Fig. 4. Simulation of adsorption/desorption parameters influence on temperature dependencies of SnO2 gas response to COECO : (1) 0.9 eV; (2) 0.8 eV; (3)
0.7 eV; (4) 0.6 eV (adapted from [42]).
and more seldom d5 (Fe2 O3 ), which are the least active with
catalytic point of view, are being used as most promising gassensing materials [34,8486]. Therefore the catalytic activity, in
spite of a coincidence of maximum gas responses temperature
and a temperature, equaled 50% of detected gas conversion, cannot explain above-mentioned choice of both d10 and d0 oxides
as base materials for conductometric gas sensors. This selection is determined by all totality of those materials properties.
For example, basing on the data, presented in [67], one can conclude that oxygen bond energy at the surface of transition-metals
oxides of the fourth period is a parameter, which better than catalytic activity defines metal oxides adaptability for solid-state
gas sensor design.
At the same time we have to admit that a choice of metal
oxide as additive for properties modification of other metal
oxides is often connected with catalytic properties of those
oxides [71,87,88]. For example, the catalytic activity to selected
gas is the most important parameter for application in membranes, used for sensor responses selectivity improvement [71].
Room temperature (RT) gas sensors is other possible field for
catalytic active metal oxide applications. In [89] it was found
that RT work-function sensors on the base of catalytically active
oxides, as CeO, Fe2 O3 , and NiO, have shown good operation
parameters.
3. Sensing material choice through their
electro-physical properties
3.1. Band gap
Pretty big band gap (Eg ) and small activation energy of the
centers, responsible for metal oxide conductivity, is an optimal combination of parameters for the materials designed for
semiconductor solid-state gas sensors. Such correlation of activation energies is necessary in order to avoid sensors operation
in the region of self-conductance. In this case the influence of
surrounding temperature on sensor parameters is reduced. At
that, as a rule, the higher operation temperature is, the bigger should be Eg . As it follows from experimental results, for
solid-state gas sensors, operating at the temperatures exceeding T > 300 C, the optimal band gap must be higher than
2.5 eV. Analyzing data, presented in [67,68,9092], one can
conclude that well-known metal oxides satisfy this requirement
(see Table 2).
For sensors, working at room temperature, Eg could be
considerably smaller [93,94]. Moreover, for example for RT
work-function sensors a small Eg may be advantage. In [29,89]
it was shown that average work-function change in the atmosphere of dry oxidizing gases (Cl2 , NO2 , SO2 ) increased when
the energy band gap of metal oxides decreased.
It is necessary to note that an opportunity to operate at higher
temperature is an important advantage of solid-state gas sensors,
because this fact allows reducing considerably the influence of
air humidity on gas-sensing characteristics. It was established
that, as a rule, the lower operating temperature is, the greater is
the sensitivity of the sensors parameters to relative air humidity
[2,34].
Table 2
Band gap of sensing materials
Table 3
Electroconductivity of some sensing materials
Material
Metal oxides
MgO, CaO, Al2 O3 , SiO2 , TeO2
SrO, Y2 O3 , HfO2 , ZrO2
BaO, La2 O3 , CeO2 , Ga2 O3
TiO2 , Nb2 O5 , Ta2 O5 , ZnO, In2 O3 , SnO2
V2 O5 , Cr2 O3 , WO3 , NiO, Fe2 O3
Co3 O4 , PdO, CuO, Sb2 O3
>6.0
56
45
34
23
12
Semiconductors
Si, InP, GaAs
SiC, GaN, diamond
1.11.41
3.275.4
Polymers
Polymers
Trans-polyacetylene
Polyphenylene
Polypyrrole
Polythiophene
0.33.5
1.4
3.4
2.73.0
2.0
Material
Metals
Semiconductors
Metal oxides
Polymers
104 to 106
108 to 103
1014 to 102
1016 to 103
tive layer (d < 20 nm) some metals, such as Pt, Au, and Ni, were
applied for this purpose [97100].
For conductometric sensors the excessively low concentration of free charge carriers (n < 1016 cm3 , i.e., < 104 to
105 Sm/cm) is also not acceptable. In nano-size structures it
reduces modulation limits of Fermi levels position and leads to
a sharp increase of the resistance of gas-sensing material.
However, it is necessary to note that for other gas sensors,
such as sorptional sensors, fiber-optic gas sensors, sensors on the
base of fluorescence effect, and so on, where the conductivity is
not a controlled parameter, there is not need to impose restrictions on electroconductivity of used materials. The materials
could be either isolator, or the ones having metal type of conductivity. For example, metals may be successfully used in devices
such as MIS sensors and work-function sensors, which exploit
the catalytic properties of metals [7]. At the same time such isolator as Al2 O3 , is good material for humidity sensor [35]. Materials
designed for high-temperature sensors (Toper > 800 C) could be
an isolator at room temperature. Conductivity in such materials
may become apparent only at high enough temperatures.
3.3. The type of conductivity
It is known that gas-sensing materials can have either n-,
or p-type of conductivity (see Table 4). Semiconductors of nand p-type have inverse direction of conductivitys change at
interaction with the same gases, which is very important fact
for their application. For materials with p-type the conductivity
rises with oxygen pressures growth, whereas for n-type oxides
it drops.
The analysis of main gas-sensing materials in respect to their
conductivity type shows that all the most effectively working gas
sensors of chemisorption type are designed on the base of metal
oxides of n-type conductivity, such as SnO2 , TiO2 , WO3 , ZnO
and In2 O3 , providing the opportunity of oxygens chemosorption. Previous research has shown that, in general, all n-oxides
are thermally stable and have possibility to work at lower oxygen
Table 4
Type of conductivity of some sensing materials
Material
Metal oxides
Semiconductors
Polymers
Type of conductivity
n
n, p
Polypyrrole, polythiophene
10
Fig. 6. The nature of processes, controlling the gas response of metal oxide gas
sensors.
Table 5
Advantages and disadvantages of sensors operating in different modes
The region of operating temperatures
Low operating temperatures Toper
< 400 C
Advantages
Disadvantages
product of the free carriers (holes) concentration and mobility terms [113]. Strong sensitivity to oxygen partial pressure
variation and negligible cross-sensitivity to temperature fluctuations make these metal oxides promising candidates for oxygen
sensors in learn burn engines [112,113].
If one could consider that the presence of structural vacancies of the lattice promotes the increase of constant of oxygen
bulk diffusion [120], it is possible to assume that for design of
sensors, in which the appearance of diffusion processes worsens
exploitation parameters, materials, which do not contain structural vacancies, are more preferable. At the same time for design
of sensors, where bulk diffusion controls sensors parameters,
the materials with native structural vacancies are preferable
[121]. It is necessary to note those perovoskite materials, investigated intensively last years for high-temperature sensors, have
these very structural properties.
3.5. Other parameters important for gas-sensing materials
Taking into account that at present a large variety of optical
methods may be used in gas sensors, including ellipsometry, luminescence, fluorescence, phosphorescence and Raman
spectroscopy, interferometry, surface plasmon and so on, one
can conclude that for gas sensor design on the base of these
methods, parameters, such as refractive index, absorbance and
fluorescence properties of analyte molecules or a chemo-optical
transducing elements will have definitive importance. For example in order to shift the operating point of the surface plasmon
resonance gas sensors towards aqueous environment, a thin high
refractive index dielectric overlayer can be employed [122]. The
use of overlayer with higher refractive indexes allows for thinner overlayer and potentially better sensor sensitivity. Analysis
of data presented in Table 6 indicates that the tantalum pentoxide, which has high refractive index and good environmental
stability, may be used for this purpose.
At the same time metal oxides such as Co3 O4 , NiO, Mn3 O4 ,
CuO and WO3 are more preferable for using in optochemical
sensors based on optical absorption change during interaction with detected gas [123,124]. The reversible absorbance
change in the visiblenear IR range and relatively fast response
make these oxides a potential candidate for optical detection
of CO, H2 , and air humidity. At that Co3 O4 -based optochemical sensors can operate already at room temperature [123].
Of course, these sensors do not possess so high sensitivity
Table 6
Refraction index of some sensing materials
Material
Semiconductors
Si, InP, GaAs
Metal oxides
Al2 O3 , SiO2
MgO, CaO, SrO
BaO, ZrO2 , HfO2 , Nb2 O5 , ZnO, SnO2 , Sb2 O3
Cr2 O3 , Fe2 O3 , NiO, Bi2 O3
TiO2 , Ta2 O5 , CuO
11
Table 7
Dielectric constants of some sensing materials
Material
Dielectric constant
Metal oxides
MgO, CaO, BaO, SiO2
Cr2 O3 , NiO, CuO, ZnO, Al2 O3
Y2 O3 , ZrO2 , V2 O5 , WO3 , SnO2
La2 O3 , HfO2 , CeO2 , Nb2 O5 , Ta2 O5
TiO2
35
510
1020
2050
>50
Semiconductors
Si, InP, GaAs
SiC
Diamond
Polymers
Polypyrrole
11.812
9.7
5.5
8
Refraction index
3.43.55
1.41.7
1.72.0
22.1
2.12.5
>2.5
Materials, destined for gas sensors, working at high temperature, have to possess high thermo-dynamic stability. The better
materials thermo-dynamic stability is, the higher are temperatures, at what chemical sensor with this material is able to work
especially at the presence in atmosphere of reducing gases.
As far as is very important to have high thermal stability, one
can judge on the base of results given in [126]. It was established
that Fe2 O3 :Pt-based sensors operating at Toper 200250 C
had maximum sensitivity to acetone to compare with SnO2 -,
12
Table 8
The parameters, characterizing a thermodynamic stability of metal oxides suitable for gas sensor applications
Material
Melting temperature ( C)
Temperature-programmed
reduction (TPR) ( C)
MgO
CaO
SrO
BaO
Y2 O3
La2 O3
TiO2
ZrO2
HfO2
CeO2
V2 O5
Nb2 O5
Ta2 O5
Cr2 O3
MoO3
WO3
Mn2 O3
Fe2 O3
Co3 O4
Rh2 O3
NiO
CuO
ZnO
Al2 O3
Ga2 O3
In2 O3
SiO2
SnO2
Bi2 O3
Sb2 O3
TeO2
28002820
25872620
24302650
19232015
601.7
635.1
590.7
553
586.2
699.7
470.8
547.4
556.8
544.6
311.9
381.1
409.9
380.0
251.7
280.3
323.9
247.7
202.3
95.3
245.2
157.0
348
558.4
360
308.6
429.1
290.5
192.6
233.2
162.6
N.R.
300
326
330
325
468
N.R.
N.R
N.R.
594
550
N.R.
340
219
575
544
184
200
288
100
278
268
N.R.
N.R
320
350
N.R
500
400
563
355
2300
1855
2690
2790
2727
690
1512
1879
23002435
795
1470
1347
1347
1562
1115
1957
1336
18001975
2050
17401805
19102000
1720
19001930
817
655
2127
Easy sublimates
T > 450 C, sublimates
13
special technological methods for local deposition of these materials in required spots [128,129].
However it is necessary to note that chemical activity of
some materials in regard to certain reagents could also be used
for high-efficient gas sensor design. As an example of those
materials there are two-phase systems such as SnO2 CuO, and
SnO2 AgO, used in gas sensors, sensitive to H2 S [130,131].
High gas response of sensors on the base of these materials is a
consequence of the following reactions:
CuO + H2 S CuS + H2 O ,
CuS + O2 CuO + SO2
(4)
or
AgO + H2 S AgS + H2 O ,
AgS + O2 AgO + SO2
(5)
(6)
14
bility of these materials are bad, and gas sensors on the base of
such materials have short life term, especially during their work
in usual atmosphere containing water and active gases. Among
other polymers undoping PPY as a semiconducting polymer, is
rather stable towards UV irradiation, which can ever increase its
conductivity [135]. However, the stability of PPYs against UV
irradiation depends on the type of dopant present in the polymer and power density of UV irradiation [136]. Moreover it was
established that UV irradiation might change the thickness and
surface roughness even PPY films [135].
Because of that fact, in spite of the wide range of gas sensors
prototypes, designed on the base of polymer films, very few of
them have found their way to the market. Even they show excellent analytical qualities, the devices are often not suitable for
industrial fabrication, because of low technological effectiveness of fabrication process, insufficient reliability and stability.
All recognize as necessary that to realize the advantages of polymers having a rare combination of electrical, electrochemical
and physical properties it is very important to increase their processability, environmental and thermal stability [93,137]. For
example, according to [138], a polyamide with high resistance
to degradation should have the following properties: (a) high
melting/softening point, (b) low weight loss as determined by
thermo-gravimetric analysis, and (c) structures that are not susceptible to degradative chain scission or intra- or intermolecular
bond formation. Intensive research is being carried out in this
direction. For example, when a segment of the aliphatic polymers main chain is replaced by a ring segment, the melting
temperature and hence, the thermal stability increases due to
the decrease in the flexibility of the polymer chain [133,138].
However, one should admit that this task with reference to gas
sensor design is pretty complicated, because it is necessary to
attain high stability while great polymers activity is being kept.
Besides, we have to remember that there are some fundamental restrictions for achievement a required thermal stability
of polymers. Information presented in [133,138] for nylon-type
polymer shows that the melting point of the polymer decreases
as the chain length increases. It means that polymers complication inevitably will be accompanied by a reducing of melting
temperature, and, therefore, by a drop in polymers stability.
Above mentioned confirms again that the problem of stability
and reliability of gas sensors is a determinant for practical use
of any gas-sensing material.
The same situation is observed for gas sensors on the base of
standard covalent semiconductors, such as Si, InP, GaAs, GaP as
well. In oxygen atmosphere it is taking place surface oxidation,
which inevitably leads to the change of electronic, adsorption,
and catalytic properties of the semiconductor surface. Gas sensors based on standard covalent semiconductor, including Si,
generally need to have an aging treatment to have reliable and
repeatable sensitivity. Even then, lifetimes of gas sensors based
on covalent semiconductors (InP, GaAs, GaP), and especially
on porous Si can be short [139]. Gas sensors on the base of
ionic compounds, such as CuBr, have unstable parameters as
well [140].
Only metal oxides and wide band semiconductors, such as
SiC, and GaN, with dielectric covering have necessary stabil-
15
functions. The last function is very important, because it determines the efficiency of chemical interactions conversion into
electrical signal. Usually this function is played by each boundary between grains, to which a double-Schottky barrier model or
neck model can be applied [13,8,56,85,156]. The resistance
depends on the surface potential modulated by concentration of
the target gas [157]. Diagram illustrating the role of necks in the
conductivity of polycrystalline metal oxide matrix is shown in
Fig. 7.
Taking into account mentioned above it becomes clear that
possibility to synthesize and deposit metal oxides with morphology and crystallographic structure optimal for achievement
maximum gas-sensing effect is important factor for application
of this material in solid-state gas sensors.
5.1. Structural parameters of sensing materials
At present, considering sensing materials, we may select
five types of materials state, differing by its structural properties. These are amorphous state, glass-state, nanocrystalline
state, polycrystalline state, and single crystal state. Every state
has its own specific peculiarities, and materials in any of these
states may be used for gas sensors design. However, in practice, nano- and polycrystalline materials have found the greatest
application in gas sensors. Exactly nano- and polycrystalline
materials have the most optimal combination of such properties as enough developed surface, cheap design technology, and
necessary stability of both structural and electro-physical properties. As it is known a specific surface area is sharply increased
with decrease of grain size. A high specific surface area and comparability of grain size (D) with the thickness of surface space
charge layer (LS ) can take great advantage for the development
of high-sensitive gas sensors [56,71,157,158]. According results
presented in [56,158,159] for achievement considerable increase
Fig. 7. Diagram illustrating the role of necks in the conductivity of polycrystalline metal oxide matrix and the potential distribution across the neck.
16
Table 9
Main advantages and disadvantages of well-known metal oxides for gas sensor applications
Material
Advantages
Disadvantages
SnO2
WO3
Ga2 O3
In2 O3
CTO (CrTiO)
Average sensitivity
Medium
Low
High
Acceptable
Low
Excellent
Low
Low
250450
Moderate
Medium
Medium
Medium
Medium
High
Good
Moderate
Moderate
Good
Excellent
High
Moderate
Reduced
Low
Reduced
Moderate
Acceptable
Acceptable
Moderate
Moderate
Acceptable
Moderate
Excellent
High
Moderate
Moderate
Enhanced
Satisfactory
High
300500
600900
200400
200450
350800
250350
300450
Low
Good
Good
Moderate
Moderate
Good
Imperfect
High
Good
High
Acceptable
Excellent
Fe2 O3
WO3
Ga2 O3
In2 O3
MoO3
TiO2
ZnO
CTO
200400
Imperfect
Fabrication
complexity
Compatibility with
standard IC
fabrication
Stability
Operating
temperature ( C)
Gas optimal for detection
Metal oxide
Table 10
Operating parameters of solid-state gas sensors on the base of metal oxides and technological peculiarities of their fabrication
Sensitivity to
air humidity
Stability in reducing
atmosphere technologies
Readiness of synthesis
and deposition
17
of works, devoted to elaboration of both deposition and synthesis technologies of various binary oxides in the form of
thin, thick, epitaxial films and ceramics using different methods
[17,184193].
Considering more complicated oxides and binary oxides,
modified by different additives, polymers and organic semiconductors, one can conclude that here there are much more
problems. For example, during polymer sputtering with use
of electronic beam their chemical decomposition is possible,
which naturally limits an opportunity of such materials application. It should be noted also that since conducting polymers
are generally insoluble and intractable, they are not amenable to
conventional methods of purification and characterization, and
some discrepancy and apparent irreproducibility may originate
from changes in preparation procedures that are sufficient to
alter the gas-sensing properties of the polymer.
An important aspect of good manufacturability of sensing material is an opportunity of its adaptation in modern
micro-electronic technology, for example during fabrication Simicromachined microhotplate array structures [147,188,194].
These devices can be adapted for a variety of applications by tuning both the composition of multiple types of active films and the
temperature cycles programmed for individual elements within
an array [188]. As last research has shown, this problem becomes
especially evident in the area of micro-miniaturization of hightemperature gas sensors. It was established that difficulties here
are connected with agglomeration of very fine metallic electrode
structure on oxide surface at high temperatures, and with film
cracks due to thermal expansion mismatch between thin film
and substrate. Therefore while choice of material for solid electrolyte gas sensor in microelectronic design, one should take
into account this specificity. According to [195], for microelectronic design such solid electrolytes as (Al,Sc)2 ((Mo,W)O4 )3
were found to be the most appropriate. They have low thermal
expansion coefficients and good chemical compatibility with
silicon technology. The most common material for macroscopic
and thick-film solid-state ionic gas sensors, zirconium oxide stabilized by ytterbium (YSZ), is well suited for integration on
silicon devices as well. At the same time the integration of alkaliion conductors with silicon technology is problematic because
of possible degradation of silicon devices due to contamination
with alkali-ions [195].
6. Outlook
As it follows from conducted analysis, the choice of a suitable
material for gas sensors should be based on good gas response,
low sensitivity to air humidity, high selectivity, low hysteresis,
high stability of parameters over the time, all range of operation
temperatures, thermal cycling, and on exposure to the various
chemicals likely to be present in the environment [34,182,196].
Therefore desired efficiency of reactions, responsible for gas
sensors sensitivity, it is necessary to achieve, taking into account
the necessity of an attainment of maximum chemical, structural,
and long-term stability of the devices parameters.
However, it is necessary to recognize that it is impossible to find a material, satisfying all possible requirements,
18
19
Table 11
Metal oxides preferable for applications in various types of gas sensors
Sensor type and sensors elements
Detected gas
Chemiresistors (semiconductor)
Capacitance
H2 ; NH3 ; C2 H5 OH
Humidity
CO2
NOx
Heterostructural
CO
H2 S
Schottky diodes
Opto-chemical
Fiber-optic
Work function (RT)
Surface plasmon resonance
Pelistors
Pyroelectric
Electronic nose
Membranes (filters)
Substrates
Electrodes
Promoters
Structure modifier (stabilizer)
Fibers
H2
H2 , CO, alcohol
H2 , CO, alcohol
CH4 , CO, Cl2
NO2 ; H2 S; NH3
Combustible gases and vapors
H2 ; CH4
Gases, vapors
ZnO; TiO2
WO3 ; Mn2 O3 ; Co3 O4 ; NiO; CuO
WO3 ; Mn2 O3 ; Co3 O4 ; NiO; CuO
NiO; Fe2 O3 ; Co3 O4
Ta2 O5 ; SiOx Ny ; TiO2
Al2 O3 ; SiO2
ZnO; LiTaO3 ; LiTiO3
SnO2 ; In2 O3 ; WO3 ; ZnO
Al2 O3 ; SiO2
Al2 O3 ; SiO2 ; BeO; LiNbO3 ; ZrO2 :Y
NiO/Ni; PdO/Pd; Al2 O3 /Pt; MgAl2 O3 /Pt
PdO; RhO; Ag2 O; CuO; Fe2 O3 ; P2 O5 ; Co3 O4 ; NiO; MnO
Al2 O3 ; SiO2 ; CaO; MgO; BaO; Y2 O3 ; La2 O3 ; Ta2 O5 ; CeO2
SiO2 ; GeO2 Sb2 O3
Electrochemical (amperometric)
Surface acoustic wave
Quartz balance
hetero-junction [22]. Composite-type sensors containing heterocontacts between the two phases fulfil this novel concept of gas
sensors. Experiments carried out in some laboratories confirmed
this assumption [219,224226].
It was established that materials, obtained as a result of this
elaboration, have their own specific advantages [224,225]. For
example, in nano-composites there are more possibilities for
control of catalytic activity of sensing matrix. It was shown also
that the introduction of TiO2 nanoparticles in polymer matrix
of poly(p-phenylenevinylene) (PPV) changes adsorption properties. Adsorption of oxygen is found to be stronger on the
PPVTiO2 nanocomposite than on pure PPV [226]. The advantage of metal oxide nanocomposites Me1 O/Me2 O, containing
two metal cations (Me1 and Me2 ), over simple nanocrystalline
oxides is associated with the redistribution of Me2 between the
bulk and the surface of Me1 O grain, depending on the redox
properties of the gas phase [219]. The appearance of additional
Me2 cation in the nanocrystalline system may result in a dramatic
change in the state of grain boundaries and in modification of the
electronic properties of the material in the presence of even trace
amounts (0.110 ppm) of reducing or oxidizing gas molecules
in the gas phase.
20
Acknowledgements
Author is thankful to Civilian Research Development Foundation (CRDF) and Moldovan Research and Development
Association (MRDA) (Grant MO-E2-3054-CS-03), Supreme
Council of the Republic of Moldova in the field of science and
advanced technology (Contract 071), and NATO (Grant CLG
980670) for financial support of his scientific research.
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