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Semiconductor gas sensors utilize porous polycrystalline resistors made of semiconducting oxides. The working principle
involves the receptor function played by the surface of each oxide grain and the transducer function played by each grain boundary.
In addition, the utility factor of the sensing body also takes part in determining the gas response. Therefore, the concepts of sensor
design are determined by considering each of these three key factors. The requirements are selection of a base oxide with high
mobility of conduction electrons and satisfactory stability (transducer function), selection of a foreign receptor which enhances
surface reactions or adsorption of target gas (receptor function), and fabrication of a highly porous, thin sensing body (utility
factor). Recent progress in sensor design based on these factors is described.
KEY WORDS: oxide semiconductor; sensor; SnO2; sensor design.
of the sensing bodies. The basic aspects of the key without additives. For example, WO3 has been used
factors and related sensor design principles are described preferably for sensing NO2 and NH3 : However, the
in more detail in the following sections. surface properties are of relatively minor importance
because the surface can be modified by depositing
foreign materials.
3. Base semiconductors
3.1. Important bulk properties
3.2. Grain size effects (transducer function)
Semiconductor gas sensors have been developed
Tin oxide powder for sensors is usually prepared by
based on limited kinds of n-type metal oxides such as
the hydrolysis of an aqueous solution of SnCl4 with an
SnO2 ; In2 O3 ; WO3 ; ZnO, and Fe2 O3 : In particular,
aqueous NH3 solution. The resulting precipitate of tin
SnO2 has been widely used. Semiconductor gas sensors
oxide hydrate is washed, dried, and calcined at a
would not have advanced so much if SnO2 were not
prescribed temperature. Tin oxide undergoes crystal
present. This is rather surprising because there are so
growth with a rise in calcination temperature. As shown
many kinds of semiconducting oxides ranging from n-
by the solid line in figure 4, the mean diameter ðdm Þ of
type to p-type, which can interact with various target
gases as widely experienced in catalytic chemistry. It is
suspected that the mobility of main carriers is of
primary importance for base semiconductors, because
it provides the proportionality constant of the change of
electrical conductivity when the number of main carriers
changes as a result of gas–solid interactions. The
mobility of conduction electrons (n-type oxides) is
reportedly 160 ðSnO2 Þ; 200 (ZnO), 100-15 ðIn2 O3 Þ; and
10 cm2 =V s ðWO3 Þ: On the other hand, the mobility of
positive holes (p-type oxide) is usually much less, as
exemplified by the value of 0:2 cm2 =V s of NiO. This
appears to be a reason why p-type oxides are not
utilized. The same reason is also applicable to some n-
type oxides. For example, TiO2 ; which has a low
mobility of conduction electrons ð0:4 cm2 =V sÞ; is not
suited to gas sensors. Instead it has been utilized as a
base semiconductor for automotive air/fuel ratio
sensors.
Another important property for a base semiconduc-
tor is chemical and thermal stability under the sensor
operating conductions. In this respect, SnO2 is the most
stable oxide among the n-type oxides widely used for
semiconductor gas sensors. No doubt, high mobility of
electrons and high stability have led to SnO2 being so
important a base semiconductor for gas sensors. Surface Figure 4. Grain size of SnO2 after calcination at various temperatures
chemical properties are also important in some cases, for several SnO2 -based powders, pure and impregnated with foreign
especially when the base semiconductor is utilized metal oxides (5 wt%).
66 N. Yamazoe, et al./Oxide semiconductor gas sensors
Table 1
Mechanism of sensitization by metal or metal oxide additive
Model
Table 3
Examples of various semiconductor gas sensors developed
Figure 11. Response vs. gas concentration correlations for devices Figure 13. Propylene sensing properties of mixed oxide catalysts for
using Co(0.5 wt%)–In2 O3 and Au(0.04 wt%)–Co(0.5 wt%)–In2 O3 selective oxidation of propylene at various temperatures. Inset shows
(250 8C). response transients at 400 8C.
N. Yamazoe, et al./Oxide semiconductor gas sensors 71
compared with the target gas (up to a few thousand that in air, 0 , is linear to the target gas concentration
ppm). The effects of reaction products are also assumed ðCA Þ; i.e.
to be negligible.
At the steady state, @CA =@t ¼ 0. If boundary condi- ðxÞ ¼ 0 ð1 þ aCA Þ ð3Þ
tions are set as CA ¼ CA;s at x ¼ 0 (surface) and
@C=@x ¼ 0 at X ¼ L (bottom), equation (1) is solved Here a is a constant, defined as gas response coefficient.
and the solution is expressed as follows: The gas response ðSÞ is expresed as follows:
sffiffiffiffiffiffiffi
CA coshð1 ÿ x=LÞm k Ra aCA
¼ ; m¼L ð2Þ S¼ ¼1þ tanh m ð4Þ
CA;s coshm DK Rg m
Here CA;s is the target gas concentration outside the Figure 20 illustrates the dependence of S on L up to
film. 300 nm by taking ðk=DK Þ1=2 as a parameter. S decreases
As shown in figure 19, the gas concentration profile with increasing L; and its tendency becomes more
depends on the magnitude of m. When m is small marked as ðk=DK Þ1=2 increases. In other words, the
ðm < 1Þ; CA at the bottom of the film is close to CA;s . highest response is obtained only when L is very small if
However, as m increases beyond unity, CA inside the ðk=DK Þ1=2 takes a significant value; thickening the film
film decreases sharply, and, ultimately at large m; CA easily leads to a decrease in S down to 1 (totally
reaches zero except for a shallow region near the insensitive).
surface. The penetration depth of the gas is reduced in Fitting of these correlations to the observed response
this way as m increases, as is well known in the field of to H2 (800 ppm in air) for the thin-film sensors (figure
heterogeneous catalysis. This means a reduction in the 17) is made in the same figure. The observed data fall
utility of the film for gas sensing, and naturally this leads fairly well on the correlation for ðk=DK Þ1=2 ¼ 10ÿ2 nmÿ1
to a reduction in gas response as described in the next if a is assumed to 1 ppmÿ1 : Remarkably the data for CO,
section. although scattered rather extensively, tend to fall near
the correlation for ðk=DK Þ1=2 ¼ 3 10ÿ2 nm when the
same value of a is assumed. The Knudsen diffusion
coefficient of CO, DK ðCOÞ;
p is about 1/4 of that of
5.3. Thickness dependence of gas response H2 ðDK ðH2 Þ=DK ðCOÞ ¼ 28=2Þ: If the other conditions
are the same, ðk=DK Þ1=2 should be about twice as large
Let us assume that the film is a uniform stack of for CO than for H2 : The value of ðk=DK Þ1=2
infinitesimally thin sheets, with electric conductance, ð3 10ÿ2 nmÞ giving the best fit to the CO response
ðxÞ; where x is depth from the surface. The conduc- data is 3 times larger than that to the H2 response data
tance of the whole film is then given by integrating ðxÞ ð10ÿ2 nmÞ; in fair agreement with the estimation. The
over the whole range of xðx ¼ 0–LÞ: An important molecular weight of the target gas influences gas
assumption is introduced here that the sheet conduc- response through diffusivity in this way. This explains
tance under exposure to the gas, ðxÞ; normalized by
Figure 20. Dependence of sensor response to H2 and CO on film Figure 21. Dependence of sensor response on temperature at various
thickness at various values of ðk=DK Þ1=2 : film thicknesses (simulated under assumptions).
74 N. Yamazoe, et al./Oxide semiconductor gas sensors
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