Sensors and Actuators B 142 (2009) 321–330

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Thin film SnO2 -based gas sensors: Film thickness influence

G. Korotcenkov a,b,∗ , B.K. Cho b,c,∗∗
a
Technical University of Moldova, Chisinau, Republic of Moldova
b
Department of Material Science and Engineering, Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-dong),
Buk-gu, Gwangju, 500-712, Republic of Korea
c
Department of Nanobio Materials and Electronics, Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-dong),
Buk-gu, Gwangju, 500-712, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: The influence of the thickness of SnO2 films deposited by a spray pyrolysis method on the operating
Received 9 June 2009 characteristics of gas sensors is analyzed in this paper. It outlines how the thickness of metal oxides
Received in revised form 1 August 2009 is an important parameter for gas sensors in determining the main operating parameters, such as the
Accepted 4 August 2009
magnitude and rate of the sensor response and the optimal operating temperature. It is also shown that
Available online 13 August 2009
the optimal film thickness of a gas sensing layer depends on the required sensor parameters.
© 2009 Elsevier B.V. All rights reserved.
Keywords:
Gas sensors
SnO2
Structure–property relationships
Thickness influence
Thin films

1. Introduction
In dealing with any type of gas sensor, establishing regularities
concerning the influence of the thickness of the gas sensing layer
on the main operating characteristics of devices is an important
task. Not many studies, however, are devoted to these regularities.
Instead, the majority of research has preferred to focus on analyz-
ing the properties of sensors that have a gas sensing layer with
a fixed thickness. Unfortunately, this does not promote a better
understanding of the observed gas sensing effects. For example, in
works which analyze the influence of the film thickness on sensor
parameters, it is possible to find results showing ambiguous conse-
quences of the film thickness change for gas sensing characteristics.
Some reports observed an increase in sensitivity to reducing gases
by increasing film thickness [1,2], while others observed a loss in
sensitivity for thicker films [3–7]. There are also results indicat-
ing that the sensor response would reach its maximum [5,7–12] or
minimum at a certain thickness [13].
∗ Corresponding author at: Department of Material Science and Engineering,
Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-
dong), Buk-gu, Gwangju, 500-712, Republic of Korea. Tel.: +82 62 970 2354;
fax: +82 62 970 2304.
∗∗ Corresponding author at: Department of Nanobio Materials and Electronics,
Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-
dong), Buk-gu, Gwangju, 500-712, Republic of Korea.
E-mail addresses: ghkoro@yahoo.com (G. Korotcenkov),
chobk@gist.ac.kr (B.K. Cho).
It has also been found that the influence of the film thickness
depends on the type of target gas. For example, in Ref. [14] it
was established that an increase in film thickness in the range of
70–300 nm promoted both a decrease in sensitivity to H2 and an
increase in sensitivity to CO. In both cases, the average size of the
SnO2 grains in the gas sensing layer was ∼6 nm. Other research
[15] has indicated that the sensitivity to some reducing gases, such
as ethanol vapor, decreased as the thickness was increased in the
range of 10–200 ␮m. At the same time, the sensitivity to other
reducing gases, such as methane, remained unchanged despite the
change in thickness. Such disagreement demonstrates once again
that the gas sensitivity of metal oxide parameters depends on many
factors, which are sometimes difficult to control [16–19].
In light of this, then, it is obvious that a deeper understanding
of the main regularities of the film thickness influence on the gas
sensing characteristics of metal oxides is necessary. At the same
time, however, it must be noted that an indicated analysis based on
the results from previously published research is not possible. As
is known, the film parameters depend greatly on the technologies
employed, which differ considerably from each other. Therefore, it
makes sense to base such an analysis only on the results obtained
for sensors fabricated using identical technology. We have previ-
ously conducted a similar analysis for the In2 O3 sensors, whose
fabrication was based on films deposited using the spray pyrol-
ysis technology [20–22]. In the present work, research related to
sensors based on SnO2 will be conducted in a similar fashion.
It is important to point out that we have previously focused on
analyzing the film thickness role in gas sensing properties of the

0925-4005/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.08.006
322 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
SnO2 films [6,13,19,23,24]. However, these published results have
not been systematized and, as a rule, in each of the articles, the
influence of the film thickness was only considered for one fixed
sensor parameter. In the present article we will try to analyze the
influence of the film thickness on a wider array of sensor parame-
ters. Besides the magnitude of the sensor response, measured at a
fixed temperature, such parameters as the dependence of the sen-
sor response on the operating temperature and the kinetics of the
sensor response will be considered. As is known, based solely on
those parameters, the suitability of the metal oxide gas sensors for
various applications can be judged [16]. We would also like to note
that, for the present analysis, we use only new experimental results
which have not been previously published or discussed.
It is necessary to note that analyzing the influence of film thick-
ness on gas sensing characteristics is a more complicated task with
sensors fabricated using thin film technology than with sensors fab-
ricated by using ceramics and thick film technologies. As has been
established, for “thin” and “thick” film gas sensors, completely dif-
ferent dependencies of the grain size on the film thickness were
observed. In both ceramic and thick film gas sensors, the size of
the SnO2 grains does not depend on the thickness of the sensing
layer. The grain size in such sensors is determined by the condi-
tions of SnO2 synthesis and the parameters of the following thermal
treatment [14,18,19]. In contrast, for thin film sensors, which were
fabricated using metal oxide deposition at temperatures higher
200–300 ◦ C, the grain size of the metal oxides is usually deter-
mined directly by the thickness of the deposited film [25,26]. The
strength of the influence on the grain size and the film morphol-
ogy of SnO2 can be seen by reviewing the results presented in our
previous works [26–28]. Such distinctions make it impossible to
apply regularities established for sensors fabricated by thick film
technology to those fabricated by thin film technology, making the
present research necessary.
2. Experimental details
SnO2 films of differing thicknesses were prepared using the
spray pyrolysis technology. The main regularities of the SnO2 depo-
sition by spray pyrolysis have been previously discussed in several
published papers [6,13,28,29]. A 0.2 M SnCl4 water based solution
was sprayed onto preheated alumina substrates, the temperature
of which was maintained at 450 ◦ C. Previous research [6,26] has
shown this deposition temperature to be optimal for forming the
gas sensing films. If deposition takes place at a higher (Tpyr > 500 ◦ C)
or lower (Tpyr < 370 ◦ C) temperatures, the SnO2 films would have a
denser structure. This high density is not optimal for application in
gas sensors, as materials need to be highly porous and permeable
[16,17].
The volumes of the sprayed tin chloride solution used for SnO2
deposition were 1 ml, 2 ml, and 7 ml and corresponded to the thick-
nesses (d): 40–50 nm, 80–90 nm, and 270–340 nm, respectively. In
our present experiments we did not use films with smaller thick-
ness because this lowest range (<40–50 nm) produces the most
ambiguity in the obtained results [3–5,7]. Films with a thickness
exceeding 350 nm were also excluded, since their gas sensing char-
acteristics are considerably worse than the characteristics of films
with smaller thickness.
For structure characterization of the studied films such meth-
ods as X-ray diffraction (XRD), transmission electron microscopy
(TEM) and the scanning electron microscopy (SEM) were applied.
For these purposes we have used a diffractometer Siemens D5000,
working with the K˛ of the Cu, a Philips CM30 Super Twin electron
microscope operating at 300 keV and a microscope Jeol JSM840,
respectively. The sample preparation methods and the measure-
ment modes have been described in detail by Arbiol in Ref. [30].
For fabrication of the gas sensor prototypes, Au electrodes were
used and the Au films were deposited by vacuum evaporation. The
distance between measured contacts was ∼2 mm, minimizing the
influence of the measurement electrodes on the gas sensing char-
acteristics. Before being measured, the samples were annealed at
500 ◦ C in an ambient air atmosphere for 15 min in order to stabilize
the sensor parameters.
Both an oxidizing gas, ozone (∼1 ppm), and a reducing gas, H2
(1000 ppm), were used as target gases. The gas sensing properties
of the deposited films were tested in a flow-type reactor, where
the tested sensors were exposed to different atmospheres with a
controlled relative humidity (35–45% or 1–2%) and a controlled
concentration of the target gas. In those measurements, we used
either air → (O3 + air) → air or air → (0.1% H2 + air) → air measure-
ment cycles. The sensor response (S) during ozone detection was
determined as the ratio S = Rgas /Rair and during H2 detection as the
ratio S = Rair /Rgas , where Rair is the resistance of the SnO2 film in
pure air and Rgas is the resistance in the air including the target gas.
All measurements were conducted at a steady-state temperature
ranging from 25 ◦ C to 450 ◦ C. In order to exclude influences from the
sensor prehistory on the research results, all measurements began
at the highest temperature of 450 ◦ C and were then decreased to
lower temperatures.
The response ( res ) and recovery times ( rec ), estimated dur-
ing “on” and “off” of the target gas correspondingly, were used for
characterization of the sensor response kinetics. Time constants of
transient processes were determined on the 0.9 level from a steady
state value of film conductivity. The methodology of these measure-
ments, including the methodology of the study of sensor response
kinetics, has been previously described [31]. During the process
of interaction with the surrounding gas, the response and recov-
ery time constants of the film conductivity relaxation have been
determined for the operating temperatures at which the time con-
stants exceeded the time of the full change of gas atmosphere in
the measuring cell. For our measuring cell, that time did not exceed
2–3 s.
3. Experimental results
3.1. Thickness influence on film morphology
A detailed structural analysis of the SnO2 films deposited by
spray pyrolysis has previously been conducted and is available in
several published papers [6,13,26,28,29]. Therefore, this paper will
provide only a short characterization of film thickness influence on
their morphology. Typical TEM images of the SnO2 films deposited
at different temperatures are shown in Fig. 1. One can see that the
SnO2 films deposited at 420–475 ◦ C (Fig. 1c) have a more developed
surface and lower crystallite packing density than the SnO2 films
deposited at other temperatures.
Typical SEM images of the films studied are shown in Fig. 2.
It can be seen that the increase of film thickness is accompa-
nied by a strong morphology transformation. We observe the
change in both the size and the shape of crystallites forming
the gas sensing layer. As the films become thicker, the grain
size also increases. For example, according to the SEM measure-
ments, the SnO2 films studied in this paper had grains with sizes
(t) equal to ∼25–30 nm, ∼40–60 nm and ∼120–160 nm for films
with thicknesses of 40–50 nm, 80–90 nm, and 270–340 nm, respec-
tively. According to the XRD measurements, the same films had
grain sizes equal to ∼21 nm, ∼33 nm and ∼51 nm, respectively.
Large discrepancies observed between the results of the SEM and
XRD measurements are explained in Refs. [26,28,29] by both the
presence of mechanical strains in the deposited films and the dis-
tinctions in methods of structural parameters’ measurement. As is
 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
Fig. 1. Cross-section TEM micrographs of the SnO2 films deposited at different tem-
peratures: (a) Tpyr = 530 ◦ C; (b) Tpyr = 330 ◦ C; (c) Tpyr = 435 ◦ C.
known, using SEM images provides the in-plane size of grains in the
top layer of analyzed films, while the grain sizes calculated from
the XRD data are thickness-averaged magnitudes. From the SEM
images, it is also clear that “thick films” (at least their top layers)
are more porous than thin films. Due to their smaller grain size, thin
films seem to be more densely packaged. Thus, presented results
of the SEM and TEM measurements confirm that the SnO2 films
deposited at 420–475 ◦ C have a more porous structure compared
with films deposited at both lower and higher pyrolysis tempera-
tures.
3.2. Thickness influence on sensor response
In analyzing the experimental data presented in the litera-
ture for all types of SnO2 -based conductometric gas sensors, it
can be concluded that, in spite of the identity of the gas sensing
material, sensors fabricated using the “thin film” and “thick film”
technologies have their own specific character of behavior dur-
ing interaction with a target gas and their own peculiarities. It has
been shown that “ceramic” and “thick film” sensors have a better
sensitivity to reducing gases [10,16,18,32,33], while “thin film” gas
sensors show a higher sensitivity to oxidizing gases [18,20,21,34].
323
Fig. 2. SEM imagers of the SnO2 films with different thickness (Tpyr = 450–475 ◦ C):
(a) d ∼ 40–50 nm; (b) d ∼ 80–90 nm; (c) d ∼ 310–380 nm.
Results obtained during the present research are also in the frame of
this indicated regularity. As the results in Fig. 3 show, an increase
of the film thickness is accompanied by both a drop in sensitiv-
ity to ozone and an increase in sensitivity to the reducing gases.
This regularity was established for a fixed operating temperature
of 300 ◦ C.
An interesting fact is that air humidity also has an opposite
influence on sensor response to H2 (CO) and ozone, as it increases
sensitivity to ozone and decreases sensitivity to reducing gases. At
present there is no generally accepted explanation for this effect
[25,34–36]. The simplest explanation is based on the humidity’
influence humidity on the initial resistance of the gas sensing layer.
As is known, the appearance of water vapor in the surrounding
atmosphere decreases the resistance of the n-SnO2 [37–40]. Due
to differences in the direction of the SnO2 resistance change dur-
ing interaction with reducing and oxidizing gases, the state with a
smaller initial resistance is better for ozone detection and worse for
CO and H2 detection. However, in reality, the mechanism of water
influence is much more complex because a change in air humidity
324 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330

Fig. 3. Influence of the film thickness on sensor response to ozone and hydrogen
(Toper = 300 ◦ C).

is also accompanied by a change in film resistance in the final state
after interaction with a target gas [35,36,41]. Due to the complexity
of the processes taking place on a hydroxylated metal oxide surface
[37,38,42–45], this paper will not discuss the peculiarities of SnO2
interaction with O3 , CO and H2 over OH-groups. Every target gas
has its own peculiarities when interacting with SnO2 and water.
Moreover, it should be noted that we do not have a definite under-
standing of these processes at this point. A description of several
possible mechanisms of the above mentioned interactions can be
found in Refs. [25,35,36,40,41,46–48].
In the frame of modern models suggested for explanation of the
gas sensing effects, grain size is one of the most important parame-
ters for gas sensing materials [49–51]. According to the conclusions
made in previous research, it is necessary to use a material with
minimal grain size in order to maximize sensitivity. Considering
that the grain size in the SnO2 films increases with the growth of
the film thickness (see Fig. 2), one can conclude that, as in the above
mentioned case, the correlation between sensitivity and grain size
occurs only for ozone detection. When gasses are reducing ones, we
obtain the opposite affect for sensor response dependence on film
thickness. Such behavior of the sensor characteristics leads to the
conclusion that the grain size in the “thin film” gas sensors plays an
important role, but at the same time, this parameter is not always
determinative. A similar conclusion has previously been made in
several published papers [1,10,17], where the influence of the films
porosity on the gas sensing effects was analyzed. For example, Dol-
bec et al. [1] and Yamazaki et al. [10] have reported that the gas
sensitivity of SnO2 films is due to the porosity rather than the
size of the crystal grains. A more detailed description of grain size
influence on gas sensing characteristics of SnO2 and In2 O3 -based
sensors can be found in a review paper devoted to the analysis of
this topic [52].
Fig. 4. The SnO2 film thickness influence on normalized S(Toper )/Smax dependen-
cies of sensor response to a reducing gas: (1) d ∼ 40–50 nm; (2) d ∼ 80–90 nm; (3)
d ∼ 280–320 nm.
al. [13] for the SnO2 -based CO sensors. In their study, they analyzed
the influence of changes in film thickness in the range of 22–170 nm
on the gas sensing characteristics of SnO2 films deposited by spray
pyrolysis. The same effect was also observed in Ref. [53] for “thick
film” gas sensors during interaction with NO2 , O3 , CO and CH4 .
Comparable sensors had films with thicknesses equal to 300 nm
and 30 ␮m. These results indicate that the established regularity of
the thickness influence on the maximum temperature of a sensor
response is really a general one for SnO2 gas sensors independent
of the type of target gas.
It is important to note that while analyzing the gas sensing char-
acteristics of ozone sensors tested over a wide range of operating
temperatures, we established that the film thickness has a specific
influence on the temperature dependence of the sensor response.
We found that an increasing the film thickness in the range of
40–350 nm, thereby shifting the sensitivity maximum towards a
range of lower temperatures, had little influence on the maximum
magnitude of sensitivity for this type of sensor. Even relatively
“thick” films were observed to have a high sensitivity to ozone.

3.3. Thickness influence on the temperature of the sensor

response maximum

During our experiments, we also established that an increase

in film thickness is accompanied by a shift in the maximum tem-
perature of the sensor response to lower operating temperatures.
Results showing these changes are given in Figs. 4 and 5.
The shift of the sensitivity maximum is observed for both the
sensors for the reducing gases (see Fig. 4), and the sensors for ozone
(see Fig. 5). This means that in both cases the film thickness influ-
ences on the temperature of the sensitivity maximum have the Fig. 5. The influence of film thickness on the temperature dependencies of sensor
same nature. A similar effect was recorded earlier by Korotcenkov et response to ozone: (1) d ∼ 40–50 nm; (2) d ∼ 80–90 nm; (3) d ∼ 280–320 nm.
 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
This once again confirms the previous statement [52] that in “thin
film” sensors the role of grain size, even for ozone detection, is not
always a determinative factor.
As shown in Fig. 5, sensors fabricated on the basis of films
with a thickness of 350 nm also have a high sensitivity to ozone.
Therefore, the previous conclusion regarding the film thickness
influence on the sensor response cannot be applied to the entire
range of operating temperatures. While analyzing the S = f(Toper )
dependences shown in Fig. 5, one can see that the S = f(t) depen-
dence presented in Fig. 3 is correct only for the temperature range
of 250–400 ◦ C. Certainly, when a wider range of operating tem-
peratures is reviewed, one can see that the influence of the film
thickness on sensor response in other working temperature ranges,
for example <220 ◦ C, could be directly opposite. However, it is clear
that the range of sensor operating temperatures of 250–400 ◦ C is
exactly the range in which it is possible to attain an acceptable com-
bination of high sensitivity and short times for both the response
and recovery processes.
It should be pointed out that the results obtained for our “thick”
film sensors (d ∼ 350 nm) cannot be extended to really thick films
with thicknesses exceeding tens and hundred of microns. As we
indicated earlier, films with such a thickness have very low sensi-
tivity to ozone [53]. Due to the high activity of ozone, the top layers
of the SnO2 film could act as a filter [54], which at a sufficient film
thickness would prevent a deep penetration of ozone into the gas
sensing material. The obtained results also cannot be applied to
the SnO2 films deposited at temperatures higher than 500 ◦ C. As
has already been established [13], the decrease in sensor response
for these films already takes place at d > 100 nm. Such behavior is in
accordance with the distinction in the structures of the SnO2 films
deposited at various temperatures described in Sections 2 and 3.1.
3.4. Thickness influence on kinetics of sensor response
Prima facie, which is the observed change of the sensor working
characteristics with an increase in the SnO2 film thickness, ensures
that sensors based on “thick” films have a considerable advantage
over sensors fabricated on thinner films. Higher sensitivity at low
operating temperatures could provide an opportunity for “thick”
film sensors to work at lower temperatures, decreasing the power
dissipated by the sensor for the attainment of the required working
temperature and, as a result, could be accompanied by an increase
in their service life. However, as a study of the kinetics of sensor
response has shown, such a change is accompanied by an increase
in response time. Fig. 6 clearly indicates that when ozone sensors
have a thicker film, they also have a greater response time,  res . This
increase is not always acceptable for real devices, especially those
assigned for in situ control.
Interestingly, as the film thickness increases, the difference
between  rec and  res becomes considerably smaller. This means
that along with the film thickness increase, changes in the pro-
cesses controlling the kinetics of sensor response also take place.
As is known, during ozone detection, a fulfillment of the correlation
 rec   res , peculiar to adsorption mechanism, is typical [21,34].
Recovery processes have a weaker dependence on film thickness.
We observed a similar situation for sensors of reducing gases
(see Fig. 7), in that the time constants also depend on the film thick-
ness. This dependence manifests as a considerable growth in the
response time of very thick sensors. The recovery time in this case,
as well as in the case of ozone sensors, shows almost no change with
an increase in film thickness. Due to this, the difference between
 rec and  res increases as the film thickness grows. If  rec and  res
are almost equal in very thin films, then  res starts to exceed  rec in
thicker films.
However, we have only observed the regularity indicated above
for sensors tested in a dry atmosphere (RH ∼1–2%). In a wet atmo-
325
Fig. 6. Film thickness influence on the time constants of the response and recovery
processes during ozone detection at Toper = 220 ◦ C in a wet atmosphere.
sphere (RH ∼35–45%), we have observed no noticeable influence
of the film thickness on the kinetics of sensor response while using
films in the thickness range of 40–350 nm. We observed very sim-
ilar behavior earlier while studying the kinetics of sensor response
for devices fabricated based on porous In2 O3 films. The growth in
time response with the increase of thickness during detection in
a wet atmosphere was observed only for films deposited under
conditions which formed denser (i.e. less gas penetrable) films.
It is necessary to note that the established regularity was also
observed for other reducing gases. In particular, we found such
dependence during the detection of CO and CH4 [24]. However,
the growth of the response time for detection of CO and CH4 with
an increase in film thickness was greater than in the case of H2
detection.
Thus, the results of the conducted research once again confirm
our previous conclusion [20]. If high-speed sensors for detection
of either reducing or oxidizing gases are required, it is necessary
to use thin films, since thicker films produce a slower rate of
response. The same conclusion can be found in Ref. [55], where
the influence of film thickness in the range of 125–400 nm on the
parameters of CO2 gas sensors was analyzed. These films were
fabricated based on BaTiO3 –CuO films deposited by a sputtering
method. In that case, the sensor response had the same magnitude
for all thicknesses used.
4. Discussion
At present two approaches are being used to explain the oper-
ating characteristics of conductometric metal oxide gas sensors.
One is an electron-chemisorption approach [23,56–61] and the
other is a diffusion-reacting approach suggested at the begin-
ning of 1990s [61–68]. According to the second approach, the
gas sensing properties of metal oxide devices are determined by
the competitive influence of gas diffusion and surface reactions
taking place in pores. Unfortunately, further work in this direc-
tion had been suspended until a diffusion-reacting approach was
explored once again in recent years in order to interpret the
obtained results [32,69–72]. Moreover, Yamazoe and co-workers
in his research tried to design a phenomenological model of metal
oxide gas sensors based on the indicated approach [14,73,74]. How-
ever, those works were focused mainly on analyzing diffusion
processes and not surface reactions. This model can therefore be
326 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
Fig. 7. The film thickness influence on response and recovery times during H2 detec-
tion at Toper = 220 ◦ C in (a) dry and (b) wet atmospheres.
characterized as a model of gas sensitivity controlled by gas diffu-
sion.
In general, both electron-chemisorption and diffusion-reacting
approaches provide explanations for the regularities obtained in
our research. The first approach does so based on the change
in the energy parameters of the adsorption–desorption processes
caused by an increase in film thickness. According to electron-
chemisorption model [17,75], these changes take place due to the
change in both the crystallographic planes faceting crystallites and
the electro-physical properties of the material conditioned by the
change in crystallite size [26–28]. The second approach provides an
explanation based on the change in distribution profiles of either
oxygen or target gas concentrations throughout the thickness of
the gas sensing layer. In thicker films, a gas with a lower diffusion
coefficient has a smaller concentration in the depth of the gas sens-
ing layer than does a gas having high diffusion coefficient [53,73]. In
this case, with an increase of film thickness, the indicated difference
rises as well. According to the second approach, an improvement
in the performance of the gas sensors may be achieved by mod-
ifying the structural properties of the gas sensing layer, such as
film porosity, instead of optimizing the energy parameters of the
chemical reactions that control the kinetics of the sensor response.
However, in the frame of a diffusion model, the temperature
shift of the sensor response maximum to lower temperatures
should be accompanied by a drop in sensitivity as the film thickness
increases [73]. According to this model [73], the sensor response
(S = Rgas /Rair ) decreases sigmoidally to 1.0 with an increase in

d k/Dk , where d is the film thickness, k is the rate constant, and
Dk is the Knudsen diffusion coefficient, which can be presented as
[76],

T
Dk = 9700 · r , (1)
M
where T is the temperature (K), r is the pore radius (cm), and M is the
molecular weight of the gas. However, as it is seen from our exper-
imental results, this correlation is not observed for our thin film
sensors. Our research has shown that sensors with either a large
or small thickness of the gas sensing layer can have equal sensor
responses. Further, for films with a thickness of 40–70 nm, it is dif-
ficult to imagine the existence of a structure in which sensitivity is
being limited by gas diffusion along the pores.
Typical structures of the thin and ultra-thin SnO2 films
deposited by spray pyrolysis on the surface of an oxidized Si sub-
strate are shown in Fig. 8. The presented images show that in films
with a thickness of 40–70 nm it is impossible to find pores with a
path at which the time of diffusion will exceed even 10−1 s. It is
necessary to note that in real experiments the response times and
recovery processes exceed tens of seconds, even at Toper > 200 ◦ C
[24,31,34]. According to a calculation based on the expressions
designed by Yamazoe and co-workers [73,74], the time necessary
for gas diffusion through the total thickness of the gas sensing layer
only at a thickness exceeding 200 ␮m can attain values, which is
comparable with the time constants of the conductivity change
observed during the process of metal oxide interaction with the
target gas. Using the diffusion model framework, it is also impos-
sible to explain the presence of a maximum in the temperature
dependence of the sensitivity for ultra-thin films.
In the frame of model, which supposes a dominant role of Knud-
sen diffusion, we also cannot explain the exponential character
of the dependence of response and recovery times on operating
temperatures observed in many experiments [24,58,61]. Therefore,
from our point of view, the electronic chemisorption model, sug-
gested in our papers [23,59,61], is a more realistic one, especially
for the thin film sensors fabricated based on gas sensing layers with
a thickness of less than 100 nm.
The chemisorption approach also more efficiently explains the
effects discussed earlier in this paper. For example, using only the
chemisorption approach, one can understand the reasons leading
to a violation in the range of temperatures <200 ◦ C of regularities,
which were established for operating temperatures of 200–400 ◦ C.
As noted in Refs. [31,50,77], at T ∼ 200 ◦ C a change takes place in
the nature of the adsorbed species dominating the SnO2 surface
and controlling the kinetics of sensor response. As was established
earlier, when T > 200 ◦ C at the SnO2 surface, oxygen is present in the
atomic chemisorbed state and when T < 200 ◦ C, a molecular form
becomes the dominant oxygen state.
However we have to admit that even in thin film gas sensors
diffusion processes participate in gas sensing effects and under cer-
tain conditions they can limit both the kinetics and magnitude of
the sensor response. Thus, the integration of the above mentioned
approaches for consideration of gas sensing effects would be the
most optimal approach and could contribute to the design of a more
general phenomenological model of solid state gas sensors. It is
necessary to point out, though, that under the diffusion processes
 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
Fig. 8. (a) TEM and (b) SEM images of the SnO2 films deposited by spray pyrolysis: (a) Tpyr = 435 ◦ C; d ∼ 40–50 nm; (b) Tpyr = 375 ◦ C; d ∼ 25–30 nm.
we refer not only to gas diffusion along pores, but also to surface
(intercrystallite) diffusion (see Fig. 9).
For sensors fabricated according to thin film technology, the
above mentioned definition of the nature of the diffusion processes
is particularly pertinent because, in spite of a considerably smaller
thickness, they do not have the porosity found in sensors fabri-
cated by thick or ceramic technologies [50]. A TEM and SEM study
of deposited films also shows a clear interface between crystal-
lites. This fact points to the absence of necks between grains, whose
overlap could be used to explain the high sensitivity of films with
a thickness of 300–350 nm during interaction with ozone [50,51].
As we have shown before, SnO2 films deposited at temperatures
higher than 350 ◦ C have columnar structure in which grains can
grow through the entire film thickness (see Fig. 1). This means that
films deposited by thin film technology have a larger contact area
between crystallites. Moreover, the comparison of the images of
films having a different thickness (see Figs. 1 and 8) shows that
the area of indicated contacts increases considerably with the film
growth. Thus, the time required for the diffusion of oxygen or oxy-
gen vacancies into intercrystallite space should increase along with
the film thickness growth. The specific character of such film struc-
ture is shown in Fig. 9.
It is necessary to note that the above mentioned view on the
nature of diffusion processes taking place in thin film gas sen-
sors was developed based on results presented by Korotcenkov
et al. [25]. This work showed that surface (intercrystallite) diffu-
sion at the interface of two crystallites, which is being controlled
in most cases by surface reactions, has the ability to determine the
Fig. 9. Models, illustrating diffusion processes dominating in films formed using (a) thick film and (b and c) thin film technologies.
327
kinetics of the sensor response of the In2 O3 -based thin film gas
sensors. Under a diffusion controlled by surface reactions, Korot-
cenkov et al. [25] understood a process in which the concentration
of oxygen, capable of diffusion and thus able to affect the metal
oxide stoichiometry at the intercrystallite interface, is controlled
by the rate of surface reactions. This last case could be used to
explain the absence of the SnO2 film thickness influence on recov-
ery time, in spite of the fact that the grain size growth takes place
with a corresponding increase of the area of intercrystallite con-
tacts. From our point of view, intercrystallite (surface) diffusion
through the change of intercrystallite metal oxide stoichiometry
can alone affect the value of the intercrystalline barrier (ϕb ), even
in cases where the relation (t/2) < L is not being executed. Here, t
is the grain size and L is the width of surface space charge region,
formed by the chemisorbed species. As established on many occa-
sions [50,51,77–79], as a rule, only a change of ϕb is responsible
for changing the conductivity of polycrystalline gas sensing films
((Rg /Ra )∼exp(ϕb )) for interaction with a target gas.
Fig. 10 shows the d influence on the film resistance normal-
ized to its thickness (R·d). It is seen that R·d grows with the d
increasing. Such behavior can be considered as a confirmation of
the of intercrystallite barriers’ responsibility for the layer resis-
tance of polycrystalline films. As the graphs in Fig. 10 show, the
clearest indicated growth for the value of R·d is observed in the
SnO2 film resistance measured in an ozone atmosphere. For the
resistance measurement in air, the growth of R·d is significantly
smaller. While measuring in an atmosphere containing a reducing
gas (H2 ), the influence of the film thickness on the value of R·d is sig-
328 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
Fig. 10. Influence of film thickness on the normalized resistance of films (R·d) mea-
sured at T = 300 ◦ C in air (1), in an atmosphere containing 0.1% H2 (2), and in an
atmosphere containing ozone (3).
nificantly smaller. It is necessary to note that the above mentioned
dependences are in agreement with the results of gas influence on
the height of surface potential barriers. As established earlier, the
interaction with ozone increases the height of the potential barrier
at the inter-grain boundary, while the interaction with hydrogen
decreases it [34,77,78,80]. Therefore, such a strong influence of the
detected gas nature on the features of R·d dependences confirms
that the conductivity of the analyzed SnO2 films in the tempera-
ture range 200–400 ◦ C is actually controlled by the resistance of
the intercrystallite barriers [79,81].
Based on the conducted analysis, we can therefore conclude
that, due to the more compact structure of the films prepared by
thin film technology, a diffusion limitation in the kinetics of sensor
response in thin film sensors can appear at considerably smaller
film thicknesses than in sensors fabricated by “thick film” technol-
ogy. For “thick film” sensors, this advantage could be realized only
after resolving the problem of small grains agglomerating in metal
oxide ceramics prepared by the thick film technology. We need to
note that the resolution of this task is quite difficult. A large contact
area between crystallites in more compact “thin film” gas sensors
could also prevent an attainment of high sensitivity. However, the
indicated shortcoming for “thin film” sensors, as a rule, starts to
appear at film thicknesses exceeding 100 nm.
5. Conclusions
The conducted research has shown that for “thin film” sensors,
the film thickness is a very important parameter and determines
their main operating characteristics, such as sensor response,
rate of response, and working temperature. Given this, choosing
the optimal thickness of the gas sensing layer (in the range of
40–350 nm) used for sensor fabrication should be determined by
three factors: (1) the required rate of sensor response, (2) the nature
of the target gas which the sensor is designed to detect, and (3) the
required operating temperature. If a high-speed sensor is needed,
it is necessary to use thin films because the thinner is the film, the
shorter the response time of metal oxide sensors is. In this case
the sensitivity is determined mainly by the efficiency of surface
reactions, while the process of gas diffusion inside the gas sens-
ing matrix, which could limit the kinetics of sensor response, does
not influence the gas sensing effects. For operating temperatures
higher than 200 ◦ C, a smaller film thickness also supports a higher
sensitivity to ozone. If the rate of sensor response is not a critical
parameter, one should use thicker films for the sensor design, which
will provide better sensitivity at lower operating temperatures.
Acknowledgements
This work was supported by the World Class University (WCU)
program at GIST (No. R31-2008-000-10026-0) and the Basic Sci-
ence Research Program through the National Research Foundation
of Korea (NRF) (No. 2009-0078928). It has been supported by a grant
provided by the Ministry of Education, Science, and Technology
(MEST) of Korea and by the project titled “Development of Mar-
itime Environmental Sensor using Nano and Photonic Technology,”
funded by the Ministry of Land, Transport and Maritime Affairs,
Korea. The authors are also thankful to Professors J.R. Morante
and A. Cornet from the University of Barcelona (Spain) and Prof.
J. Schwank from the University of Michigan (USA) for their help in
structural characterization of the studied SnO2 films, as well as to
I. Blinov from the Technical University of Moldova for his help in
gas sensor characterization and Dr. A. England from the National
Fusion Research Institute (Korea) for useful discussions.
References
[1] R. Dolbec, M.A. El Khakani, A.M. Serventi, R.G. Saint-Jacques, Influence of the
nanostructural characteristics on the gas sensing properties of pulsed laser
deposited tin oxide thin films, Sens. Actuators B 93 (2003) 566–571.
[2] T.-R. Ling, C.-M. Tsai, Influence of nano-scale dopants of Pt, CaO and SiO2 , on
the alcohol sensing of SnO2 thin films, Sens. Actuators B 119 (2006) 497–503.
[3] L. Bruno, C. Pijolat, R. Lalauze, Tin dioxide thin-film gas sensor prepared by
chemical vapour deposition. Influence of grain size and thickness on the elec-
trical properties, Sens. Actuators B: Chem. 18–19 (1994) 195–199.
[4] T. Mochida, K. Kikuchi, T. Kondo, H. Ueno, Y. Matsuura, Highly sensitive and
selective H2 S gas sensor from r.f. sputtered SnO2 , thin film, Sens. Actuators B
24–25 (1995) 433–437.
[5] P. Montmeat, R. Lalauze, J.-P. Viricelle, G. Tournier, C. Pijolat, Model of the thick-
ness effect of SnO2 thick film on the detection properties, Sens. Actuators B 103
(2004) 84–90.
[6] G. Korotcenkov, V. Brinzari, M. DiBattista, J. Schwank, A. Vasiliev, Peculiarities
of SnO2 thin film deposition by spray pyrolysis for gas sensor application, Sens.
Actuators B 77 (2001) 244–252.
[7] J. KIiiber, M. Ludwig, H.A. Schneider, Effects of thickness and additives on thin-
film SnO2 gas sensors, Sens. Actuators B 3 (1991) 69–74.
[8] G. Sberveglieri, Classical and novel techniques for the preparation of SnO2 thin-
film gas sensors, Sens. Actuators B 6 (1992) 239–247.
[9] G. Williams, G.S.V. Coles, Gas sensing properties of nanocrystalline metal oxide
films, in: Sensors Applications VII, IOP, London, 1995, pp. 69–73.
[10] T. Yamazaki, H. Okumura, C.-J. Jin, A. Nakayama, T. Kikuta, N. Nakatani, Effect
of density and thickness on H2 -gas sensing property of sputtered SnO2 films,
Vacuum 77 (2005) 237–243.
[11] T. Suzuki, T. Yamazaki, M. Azumaya, Hydrogen gas sensing properties in poly-
crystalline tin oxide films of submicron thickness, J. Ceram. Soc. Jpn. 97 (1989)
1268–1273.
[12] S.-S. Park, J.D. Mackenzie, Thickness and microstructure effects on alcohol sens-
ing of tin oxide thin films, Thin Solid Films 274 (1996) 154–159.
[13] G. Korotcenkov, V. Brinzari, J. Schwank, A. Cerneavschi, Possibilities of aerosol
technology for deposition of SnO2 -based films with improved gas sensing char-
acteristics, Mater. Sci. Eng. C 19 (1–2) (2001) 73–77.
[14] G. Sakai, N.S. Baik, N. Miura, N. Yamazoe, Gas sensing properties of tin oxide
thin films fabricated from hydrothermally treated nanoparticles. Dependence
of CO and H2 response on film thickness, Sens. Actuators B 77 (2001) 116–121.
[15] L. de Angelis, R. Riva, Selectivity and stability of a tin dioxide sensor for methane,
Sens. Actuators B 28 (1995) 25–29.
[16] G. Korotcenkov, Metal oxides for solid state gas sensors. What determines our
choice? Mater. Sci. Eng. B 139 (2007) 1–23.
[17] G. Korotcenkov, The role of morphology and crystallographic structure of metal
oxides in response of conductometric-type gas sensors, Mater. Sci. Eng. R 61
(2008) 1–39.
[18] G. Korotcenkov, Gas response control through structural and chemical modifi-
cation of metal oxides: state of the art and approaches, Sens. Actuators B 107
(2005) 209–232.
[19] V. Brinzari, G. Korotcenkov, V. Golovanov, Factors influencing the gas sensing
characteristics of tin dioxide films deposited by spray pyrolysis: understanding
and possibilities for control, Thin Solid Films 391 (2) (2001) 167–175.
[20] G. Korotcenkov, V. Brinzari, A. Cerneavschi, M. Ivanov, V. Golovanov, A. Cor-
net, J. Morante, A. Cabot, J. Arbiol, The influence of film structure on In2 O3 gas
response, Thin Solid Films 460 (2004) 308–316.
 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330
[21] G. Korotcenkov, A. Cerneavschi, V. Brinzari, A. Vasiliev, A. Cornet, J. Morante, A.
Cabot, J. Arbiol, In2 O3 films deposited by spray pyrolysis as a material for ozone
gas sensors, Sens. Actuators B 99 (2004) 304–310.
[22] G. Korotcenkov, V. Brinzari, A. Cerneavschi, M. Ivanov, A. Cornet, J. Morante,
A. Cabot, J. Arbiol, In2 O3 films deposited by spray pyrolysis: gas response to
reducing (CO, H2 ) gases, Sens. Actuators B 98 (2004) 236–243.
[23] V. Brinzari, G. Korotcenkov, J. Schwank, Optimization of thin film gas sensors for
environmental monitoring through theoretical modeling, In: S. Buettgenbach
(Ed.), Chemical Microsensors and Applications II, Proc. of SPIE, vol. 3857, 1999,
pp. 186–197.
[24] G. Korotchenkov, V. Brynzari, S. Dmitriev, Kinetics characteristics of SnO2
thin film gas sensors for environmental monitoring. In: S. Buettgenbach
(Ed.), Chemical Microsensors and Applications, Proc. of SPIE, vol. 3539, 1998,
pp. 196–204.
[25] G. Korotcenkov, V. Brinzari, J.R. Stetter, I. Blinov, V. Blaja, The nature of processes
controlling the kinetics of indium oxide-based thin film gas sensor response,
Sens. Actuators B 128 (2007) 51–63.
[26] G. Korotcenkov, A. Cornet, E. Rossinyol, J. Arbiol, V. Brinzari, Y. Blinov, Faceting
characterization of SnO2 nanocrystals deposited by spray pyrolysis from
SnCl4 –5H2 O water solution, Thin Solid Films 471 (2005) 310–319.
[27] E. Elangovan, M.P. Singh, K. Ramamurthi, Studies on structural and electrical
properties of spray deposited SnO2 :F thin films as a function of film thickness,
Mater. Sci. Eng. B 113 (2004) 143–148.
[28] V. Brinzari, G. Korotcenkov, J. Schwank, V. Lantto, S. Saukko, V. Golo-
vanov, Morphological rank of nano-scale tin dioxide films deposited by
spray pyrolysis from SnCl4 ·5H2 O water solution, Thin Solid Films 408 (2002)
51–58.
[29] G. Korotcenkov, M. DiBattista, J. Schwank, V. Brinzari, Structural characteriza-
tion of SnO2 gas sensing films deposited by spray pyrolysis, Mater. Sci. Eng. B
77 (2000) 33–39.
[30] J. Arbiol, Metal additive distribution in TiO2 and SnO2 semiconductor gas sen-
sor nanostructured materials, PhD Thesis, University of Barcelona, Barcelona,
Spain, 2001.
[31] G. Korotcenkov, M. Ivanov, I. Blinov, J.R. Stetter, Kinetics of In2 O3 -based thin film
gas sensor response: the role of “redox” and adsorption/desorption processes
in gas sensing effects, Thin Solid Films 515 (2007) 3987–3996.
[32] Y. Shimuzu, T. Maekawa, T. Nakamura, M. Egashira, Effects of gas diffusivity
and reactivity on gas sensing properties of thick film SnO2 -based sensors, Sens.
Actuators B 46 (1998) 163–168.
[33] N. Yamazoe, New approaches for improving semiconductor gas sensors, Sens.
Actuators B 5 (1991) 7–19.
[34] G. Korotcenkov, I. Blinov, M. Ivanov, J.R. Stetter, Ozone sensors on the base
of SnO2 thin films deposited by spray pyrolysis, Sens. Actuators B 120 (2007)
679–686.
[35] G. Korotcenkov, I. Blinov, V. Brinzari, J.R. Stetter, Effect of air humidity on
gas response of SnO2 thin film ozone sensors, Sens. Actuators B 122 (2007)
519–526.
[36] G. Korotcenkov, V. Brinzari, Y. Boris, M. Ivanov, J. Schwank, J. Morante, Surface
Pd doping influence on gas sensing characteristics of SnO2 thin films deposited
by spray pyrolysis, Thin Solid Films 436 (2003) 119–126.
[37] M. Batzill, Surface science studies of gas sensing materials: SnO2 , Sensors 6
(2006) 1345–1366.
[38] D.F. Cox, S. Semancik, P.D. Szuromi, Structural and electronic-properties of
clean and water dosed SnO2 (1 1 0), J. Vac. Sci. Technol. A 4 (1986) 627–628.
[39] J.F. Boyle, K.A. Jones, The effects of CO, water vapor and surface temperature on
the conductivity of a SnO2 gas sensor, J. Electronic Mater. 6 (1977) 717–720.
[40] G. Korotchenkov, V. Brynzari, S. Dmitriev, Electrical behavior of SnO2 thin films
in humid atmosphere, Sens. Actuators B 54 (1999) 197–201.
[41] S.H. Hahn, N. Bârsan, U. Weimar, S.G. Ejakov, J.H. Visser, R.E. Soltis, CO sensing
with SnO2 thick film sensors: role of oxygen and water vapour, Thin Solid Films
436 (2003) 17–24.
[42] A. Verdaguer, G.M. Sacha, H. Bluhm, M. Salmeron, Molecular structure of
water at interfaces: wetting at the nanometer scale, Chem. Rev. 106 (2006)
1478–1510.
[43] J. Gonialowski, M.J. Gilan, The adsorption of H2 O on TiO2 and SnO2 (1 1 0)
studied by first-principles calculations, Surf. Sci. 350 (1996) 145–158.
[44] N. Yamazoe, J. Fuchigami, M. Kishikawa, T. Seiyama, Interactions of tin oxide
with O2 , H2 O and H2 , Surf. Sci. 86 (1979) 335–344.
[45] M. Egashira, M. Nakashima, S. Kawasumi, T. Seiyama, Temperature pro-
grammed desorption study of water adsorbed on metal oxides. 2. Tin oxide
surfaces, J. Phys. Chem. 85 (1981) 4125–4130.
[46] D. Koziej, N. Barsan, U. Weimar, J. Szuber, K. Shimanoe, N. Yamazoe,
Water–oxygen interplay on tin dioxide surface: implication on gas sensing,
Chem. Phys. Lett. 410 (2005) 321–323.
[47] R. Ionescu, A. Vancu, C. Moise, A. Tomescu, Role of water vapour in the interac-
tion of SnO2 gas sensors with CO and CH4 , Sens. Actuators B 61 (1999) 39–42.
[48] V. Golovanov, T. Pekna, A. Kiv, V. Litovchenko, G. Korotcenkov, V. Brinzari, A.
Cornet, J. Morante, The influence of structural factors on sensitivity of SnO2 -
based gas sensors to CO in humid atmosphere, Ukr. Phys. J. 50 (4) (2005)
374–380.
[49] N. Matsunaga, G. Sakai, K. Shimanoe, N. Yamazoe, Diffusion equation-based
study of thin film semiconductor gas sensor-response transient, Sens. Actuators
B 83 (2002) 216–221.
[50] N. Barsan, M. Schweizer-Berberich, W. Göpel, Fundamental and practical
aspects in the design of nanoscaled SnO2 gas sensors: a status report, Fresenius
J. Anal. Chem. 365 (1999) 287–304.
329
[51] X. Wang, S.S. Yee, W.P. Carey, Transition between neck-controlled and grain-
boundary-controlled sensitivity of metal-oxide gas sensors, Sens. Actuators B
24–25 (1995) 454–457.
[52] G. Korotcenkov, S.D. Han, B.K. Cho, V. Brinzari, Grain size effects in sensor
response of nanostructured SnO2 - and In2 O3 -based conductometric gas sensor,
Crit. Rev. Solid State Mater. Sci. 34 (1–2) (2009) 1–17.
[53] Th. Becker, S. Ahlers, C. Bosch-v.Braunmühl, G. Müller, O. Kiesewetter, Gas sens-
ing properties of thin- and thick-film tin-oxide materials, Sens. Actuators B 77
(2001) 55–61.
[54] C. Pijolat, J.P. Viricelle, G. Tournier, P. Montmeat, Application of membranes
and filtering films for gas sensors improvements, Thin Solid Films 490 (2005)
7–16.
[55] J. Herran, G.G. Mandayo, E. Castano, Solid state gas sensor for fast carbon dioxide
detection, Sens. Actuators B 129 (2008) 705–709.
[56] J. Ding, T.J. McAvoy, R.E. Cavicchi, S. Semancik, Surface state trapping model for
SnO2 -based microplate sensor, Sens. Actuators B 77 (2001) 597–613.
[57] H. Geistlinger, Electron theory of thin-film gas sensors, Sens. Actuators B 17
(1993) 47–60.
[58] H. Geistlinger, Accumulation layer model for Ga2 O3 thin-film gas sensors
based on the Volkenstein theory of catalysis, Sens. Actuators B 18–19 (1994)
125–131.
[59] V. Brynzari, G. Korotchenkov, S. Dmitriev, Theoretical study of semiconductor
thin film gas sensitivity: attempt to consistent approach, J. Electron Technol.
33 (2000) 225–235.
[60] V. Brinzari, G. Korotcenkov, J. Schwank, Y. Boris, Chemisorptional approach to
kinetic analysis of SnO2 :Pd-based thin film gas sensors (TFGS), J. Optoelectron.
Adv. Mater. 4 (1) (2002) 147–150.
[61] V. Brynzari, G. Korotchenkov, S. Dmitriev, Simulation of thin film gas sensor
kinetics, Sens. Actuators B 61 (1–3) (1999) 143–153.
[62] D.E. Williams, K.F.E. Pratt, Theory of self-diagnostic sensor array devices
using gas-sensitive resistors, J. Chem. Soc., Faraday Trans. 91 (1995)
1961–1966.
[63] J.W. Gardner, A diffusion-reaction model of electrical conduction in tin oxide
gas sensors, Semicond. Sci. Technol. 4 (1989) 345–350.
[64] J.W. Gardner, Electrical conduction in solid-state gas sensors, Sens. Actuators
18 (1989) 373–387.
[65] J.W. Gardner, A non-linear diffusion-reaction model of electrical conduction in
semiconductor gas sensors, Sens. Actuators B 1 (1999) 166–170.
[66] J.W. Gardner, M. Iskandarani, Effect of electrode geometry on gas sensitivity of
lead phthalocyanine thin films, Sens. Actuators B 9 (1992) 133–142.
[67] U. Jain, A.H. Harker, A.M. Stoneham, D.E. Williams, Effect of electrode geometry
on sensor response, Sens. Actuators B 2 (1990) 111–114.
[68] D.E. Williams, G.S. Hensham, K.F.E. Pratt, Reaction-diffusion effects and system-
atic design of gas-sensitive resistors based on semiconducting oxides, J. Chem.
Soc., Faraday Trans. 91 (23) (1995) 4299–4307.
[69] H. Lu, W. Ma, J. Gao, J. Li, Diffusion-reaction theory for conductance
response in metal oxide gas sensing thin films, Sens. Actuators B 66 (2000)
228–231.
[70] F. Rettig, R. Moos, C. Plog, Sulfur adsorber for thick-film exhaust gas sensors,
Sens. Actuators B 93 (2003) 36–42.
[71] K. Darcovich, F.F. Garcia, C.A. Jeffrey, J.J. Tunney, M.L. Post, Coupled microstruc-
tural and transport effects in n-type sensor response modeling for thin layers,
Sens. Actuators A 147 (2008) 378–386.
[72] P. Boeker, O. Wallenfang, G. Horner, Mechanistic model of diffusion and reac-
tion in thin sensor layers—the DIRMAS model, Sens. Actuators B 83 (2002)
202–208.
[73] G. Sakai, N. Matsunaga, K. Shimanoe, N. Yamazoe, Theory of gas-diffusion con-
trolled sensitivity for thin film semiconductor gas sensor, Sens. Actuators B 80
(2001) 125–131.
[74] N. Matsunaga, G. Sakai, K. Shimanoe, N. Yamazoe, Formulation of gas dif-
fusion dynamics for thin film semiconductor gas sensor based on simple
reaction–diffusion equation, Sens. Actuators B 96 (2003) 226–233.
[75] F.F. Volkenstein, The Electronic Theory of Catalysis on Semiconductors, Perga-
mon, Oxford, 1963.
[76] C.N. Satterfield, Mass Transfer in Heterogeneous Catalysis, MIT Press, Cam-
bridge, MA, 1970.
[77] N. Barsan, D. Koziej, U. Weimar, Metal oxide-based gas sensor research: how
to? Sens. Actuators B 121 (2007) 18–35.
[78] A. Karthigeyan, R.P. Gupta, K. Scharnagl, M. Burgmair, M. Zimmer, S.K. Sharma,
I. Eisele, Low temperature NO2 sensitivity of nano-particulate SnO2 film work
function sensors, Sens. Actuators B 78 (2001) 69–72.
[79] K.-D. Schierbaum, Engineering of oxide surfaces and metal/oxide interfaces for
chemical sensors: recent trends, Sens. Actuators B 24–25 (1995) 239–247.
[80] B. Yea, R. Konishi, T. Osaki, S. Abe, H. Tanioka, K. Sugahara, Analysis of the
sensing mechanism of tin dioxide thin film gas sensors using the change of
work function in flammable gas atmosphere, Appl. Surf. Sci. 100/101 (1996)
365–369.
[81] A. Chandra Bose, P. Thangadurai, S. Ramasamy, Grain size dependent electrical
studies on nanocrystalline SnO2 , Mater. Chem. Phys. 95 (2006) 72–78.
Biographies
G. Korotcenkov received his PhD in physics and technology of semiconductor mate-
rials and devices from Technical University of Moldova in 1976 and his Habilitat
degree in physics and mathematics from Academy of Science of Moldova in 1990.
330 G. Korotcenkov, B.K. Cho / Sensors and Actuators B 142 (2009) 321–330

Currently he is a research professor at Gwangju Institute of Science and Technol-
ogy (GIST) in Korea. Long time his research activity was focused on the study of
Schottky barriers, MOS structures, and various photoreceivers on the base of III-Vs
compounds. His present scientific interests include material sciences, focusing on
metal oxide film deposition and characterization, surface science, and thin film gas
sensor design.
B.K. Cho is a professor in Department of Nanobio Materials and Electronics, and
Department of Materials Science and Engineering at Gwangju Institute of Science
and Technology (GIST) in Korea. He received his PhD in physics and astronomy
from Iowa State University, USA in 1995. His current research project is focused on
material science and the applications of nano-spin devices, especially development
of biosensors using magnetic thin film technology.