Sensors and Actuators B 123 (2007) 1090–1095

Highly sensitive SnO2 thin film NO2 gas sensor

operating at low temperature
Jaswinder Kaur a , Somnath C. Roy b , M.C. Bhatnagar a,∗
a Thin Film Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India
b Amity School of Engineering, Amity University Campus, Sector 125, Noida 201302, Uttar Pradesh, India

Received 17 July 2006; received in revised form 13 November 2006; accepted 17 November 2006
Available online 22 December 2006

Abstract
Thin films of pure nano-crystalline SnO2 and WO3 -doped SnO2 in different concentrations (3 wt.% and 5 wt.%) are deposited using sol–gel
spin coating technique on glass substrates. The structural and morphological properties of these films are investigated using XRD, TEM and AFM.
The sensitivity and selectivity of these films are tested to different reducing and oxidizing gases such as SO2 , NH3 , NO2 and ethanol. A SnO2 thin
film with 5 wt.% WO3 shows very high responses to NO2 (four orders of magnitude in the value of (Rg − Ra )/Ra ; Rg and Ra are the resistance in
NO2 and in air, respectively) and excellent selectivity for NO2 gas at a low operating temperature of 150 ◦ C. The effect of WO3 on the sensing
characteristics of these films towards NO2 is discussed.
© 2006 Elsevier B.V. All rights reserved.

Keywords: SnO2 thin film; NO2 ; Gas sensors; Low operating temperature

1. Introduction reduction of grain size, addition of catalysts/promoters and fil-

For environmental and safety purposes, gas sensors are
required for monitoring poisonous and hazardous gases such
as NO2 , CO, SO2 , etc. in domestic as well as industrial areas.
Among semiconductor oxide gas sensors, tin oxide (SnO2 ) is a
well known n-type semiconducting oxide that has been widely
used for the detection of a wide spectrum of oxidizing and
reducing gases in an operating temperature range of 200–500 ◦ C
[1,2]. This oxide material has high reactivity towards reducing
gases at relatively low operating temperature, easy adsorption of
oxygen on its surface because of its natural non-stoichiometry,
stable rutile phase and many more desirable attributes such as
cheapness and simplicity [3]. The presence of oxidizing gases
decreases the film conductance, whereas the presence of reduc-
ing gases increases it [4]. The range of application of these types
of gas sensors is limited by their poor selectivity, sensitivity
and response time. In order to enhance the sensing properties
of SnO2 films, various methods have been adopted such as
∗Corresponding author.
E-mail addresses: mann jaswinder@yahoo.com (J. Kaur),
mukesh1ch@yahoo.co.in (M.C. Bhatnagar).
ters, addition of dopants and using mixed metal oxides [5–8].
Besides all these efforts, the problems due to poor selectivity,
long time stability and high operating temperature are still there.
Most of the commercial and industrial applications require the
gas sensors to be operated at lower temperatures (especially at
room temperature) to avoid the instability in the nano-crystallite
size and hence to increase the robustness and life of sen-
sors [9]. In spite of this, very few attempts [10,11] have been
made to develop nano-crystalline SnO2 sensors operating at low
temperature.
A huge amount of research activity has been carried out on
tin oxide in order to improve the sensitivity and selectivity of
tin oxide-based gas sensors. Both WO3 and SnO2 are n-type
semiconductors, with wide band gap donors being related to
the non-stoichiometry, and are well known for NO2 detection.
Most of the work for NO2 detection is based on thick film tech-
nology [12,13], where the optimum operating temperature was
reported to be 200–300 ◦ C [14,15] or even at higher temper-
atures in case of pure and activated WO3 nano-particle films
[16,17]. The maximum gas response reported for these sensors
is of the order of (Rg –Ra )/Ra ≈ 102 with a very good selectivity
[18]. In the present study, an attempt has been made to improve
the selectivity and sensitivity of tin oxide-based NO2 gas sensors

0925-4005/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.11.031
 J. Kaur et al. / Sensors and Actuators B 123 (2007) 1090–1095
along with lowering of operating temperature by adding dopants
and modifying the structural and morphological properties.
2. Experimental detail
Tin oxide thin films were prepared by a sol–gel spin coating
process using SnCl4 ·5H2 O, ethyl alcohol and de-ionized water
as precursors. After refluxing for 48 h at room temperature using
a magnetic stirrer, a homogeneous mixture of precursors was
formed with hydrolysis and condensation processes. This step
was followed by an ageing process, which was used to stabilize
the pH, by leaving it in open air for 24 h. WO3 -doped sols with
two different concentrations (3 wt.% and 5 wt.%) were prepared
by adding an appropriate amount of ammonium tungstate in a
SnCl4 ·5H2 O solution in its initial preparation stage. Pure SnO2
and WO3 -doped SnO2 thin films were deposited on glass sub-
strates using a sol–gel spin coating process with a spinning speed
of 4000 rpm for 40 s. Each deposited layer was pre-sintered at
200 ◦ C for 20 min before depositing the next layer. Post-sintering
was done at 450 ◦ C for 6 h.
The thickness of the deposited films was measured by using a
surface profilometer and was found approximately 120–130 nm.
The structural analysis was done using a Philips ‘Xpert’ model
glancing angle X-ray diffractometer (GAXRD) in the 2θ range
of 20–80◦ . Surface topography and morphology were studied
by atomic force microscopy (AFM) using digital Instrument
Nanoscope III, transmission electron microscopy (TEM) with
Philips model CM12 operating at 100 kV. On the surface of these
films a finger-like interdigitated gold pattern was deposited for
electrodes.
Gas sensing experiments were performed by using a static
method with a controlled gas flow through mass flow controllers
attached to the sensing setup. Fig. 1 represents the block dia-
gram of the gas sensing setup used. The operating temperature
was varied from 100 ◦ C to 250 ◦ C in order to find out the opti-
Fig. 1. Gas sensing setup for measuring sensing characteristics.
1091
Fig. 2. Glancing angle X-ray diffraction patterns of undoped SnO2 , 3 wt.% and
5 wt.% WO3 -doped SnO2 thin films.
mum working temperature of these deposited films. Change in
resistance, with and without target gas, was measured using a
computer-interfaced Fluke 187/189 True RMS digital multime-
ter, to determine the change in resistance. The sensor responses
for oxidizing and reducing gases are defined as
Rg − Ra
So = (for oxidizing gas) and
Ra
Ra − Rg
Sr = (for reducing gas)
Rg
where Rg is the resistance in the presence of a target gas and Ra
is the resistance in air.
To investigate the selectivity of the sensors for NO2 gas, the
responses to other reducing gases such as sulphur dioxide (SO2 ),
ethanol (C2 H5 OH) and ammonia (NH3 ) of the same quantity
were examined and compared with that of NO2 gas.
3. Results and discussion
Thin films of about 120 nm thicknesses of pure tin oxide,
3 wt.% and 5 wt.% WO3 -doped tin oxides were investigated for
their structural and surface morphological properties. Fig. 2 dis-
plays the XRD patterns obtained from the doped and undoped
SnO2 thin films. These films were polycrystalline in nature. The
prominent peaks corresponding to (1 1 0), (1 0 1) and (2 1 1)
crystal lattice planes and all other smaller peaks coincide
with the corresponding peaks of the rutile structure of SnO2
given in the standard data file (JCPDS File no.41–1445). No
peak corresponding to WO3 was observed. It is also noted
that the full width at half maximum (FWHM) of these peaks
increases with an increase in dopant concentration of WO3 .
The average particle size estimated by Scherrer’s formula using
FWHM of main prominent peaks indicates a decrease in par-
ticle size as a result of incorporation of WO3 in the SnO2
films.
Fig. 3 describes variations of d/d with Nelson–Riley factor
(NRF) [19] for SnO2 films with different WO3 concentrations
(shown in the figure). Qualitatively, the large variations in d/d
1092 J. Kaur et al. / Sensors and Actuators B 123 (2007) 1090–1095

Fig. 3. NRF plots for undoped, 3 wt.% and 5 wt.% WO3 -doped SnO2 films.

values indicate a large amount of stacking faults present in the

samples [20]. The standard data for d values of SnO2 were taken
from JCPDS file no. 001-0625. Further, the lattice parameter
‘a’ was estimated from extrapolated NRF data. It is found that
the value of ‘a’ increased from 0.4730 nm to 0.4784 nm and
0.4792 nm when the WO3 content increased from 0 wt.% to
3 wt.% and 5 wt.%, respectively. It can, therefore, be inferred
that the W incorporation led to an increase in the stacking fault
density in the SnO2 films along with an increase in the lattice
parameter.
The surface morphology of these films is shown in Fig. 4
by the transmission electron microscopy (TEM) under the same
magnification. The micrographs clearly indicate that the average
crystallite size decreases with doping. The micrograph of the
undoped SnO2 film shows agglomerated particles, whereas with
doping the particles acquire definite shape and reduction in size.
Both the XRD spectra and the TEM micrographs conclude that
the addition of WO3 restricts the growth of crystallites in the
SnO2 films.
Atomic force microscopy (AFM) micrographs of undoped,
3 wt.% and 5 wt.% WO3 -doped SnO2 films are shown in Fig. 5.
The particle distribution in these films is found uniform with a
decrease in average particle size along with an increase in WO3
doping concentration. The root mean square values of rough-
ness are found increasing with an increase in WO3 amount in
these films. For undoped, 3 wt.% and 5 wt.% WO3 -doped films
the root mean square (RMS) values of roughness was found to
be 0.88 nm, 2.3 nm and 3.84 nm, respectively. Here it has been
observed that the undoped film has agglomerated particles as
compared to the doped films with uniform distribution of smaller
size particles. Along with this reduction in size the shape of these Fig. 4. TEM micrographs of (a) undoped, (b) 3 wt.% and (c) 5 wt.% WO3 -doped
particles also gets changed with doping of tungsten trioxide in SnO2 thin films.
the SnO2 films. This is a further confirmation of the increase in
stacking fault density. gas at an optimum temperature of 150 ◦ C for sensing NO2
Gas sensing experiments were performed at different temper- gas whereas the undoped SnO2 film senses the gas at a higher
atures in order to find out the optimum operating temperature operating temperature of about 300 ◦ C. Fig. 6 shows the vari-
of these films for NO2 gas sensing. Before starting these exper- ation of response with operating temperature for undoped and
iments each sample was stabilized at the testing temperature both (3 wt.% and 5 wt.%) WO3 -doped SnO2 films. The 5 wt.%
for 4 h. All these experiments were performed with 500 ppm WO3 -doped film shows the maximum response of about 33,400
 J. Kaur et al. / Sensors and Actuators B 123 (2007) 1090–1095 1093

Fig. 6. Response to 500 ppm NO2 gas of undoped, 3 wt.% and 5 wt.% WO3 -
doped SnO2 films.

Table 1a
Responses to 500 ppm NO2 gas of undoped, 3 wt.% and 5 wt.% WO3 -doped
SnO2 thin films
Temperature 3 wt.% doped Response 5 wt.% Undoped
(◦ C) SnO2 doped SnO2 SnO2

100 400 2,210 10

125 480 5,430 9
150 650 33,359 11
175 5,000 135 13
200 17,000 70 13
215 234 87 23
235 2,404 872 22
250 2,033 120 40

Fig. 5. AFM micrographs of (a) undoped (b) 3 wt.% and (c)5 wt.% WO3 -doped
SnO2 thin film.

at 150 ◦ C for NO2 gas. Table 1a represents the responses of

these WO3 -doped and undoped films at different temperatures.
Among all these tested temperatures the response of the 5 wt.%-
doped sample was found higher than that of the 3 wt.%-doped Fig. 7. Response vs. time plot of different gases (500 ppm) for 5 wt.% WO3 -
film. For this reason only, further study was carried out for the doped SnO2 thin film at 150 ◦ C.
5 wt.% WO3 -doped film. Selectivity of the 5 wt.% WO3 -doped
Table 1b
SnO2 films was tested using various gases such as ammonia Responses of 5 wt.% WO3 -doped SnO2 thin film to different gases of 500 ppm
(NH3 ), ethanol (C2 H5 OH) and sulphur dioxide (SO2 ) and is
Gas Response
shown in Fig. 7. The sensitivity values for these gases (500 ppm
for all gases) for the 5 wt.%-doped SnO2 film is tabulated in NO2 33,359
Table 1b. C2 H5 OH 1.5
SO2 22
It can be inferred that the 5 wt.% WO3 -doped SnO2 film
NH3 0.21
is highly selective for NO2 gas at a temperature of 150 ◦ C as
1094 J. Kaur et al. / Sensors and Actuators B 123 (2007) 1090–1095
Fig. 8. Response transient to 500 ppm NO2 of (a) 5 wt.% and (b) 3 wt.% WO3 -
doped SnO2 thin film at 150 ◦ C.
compared to all other tested gases. The response and recov-
ery times of the 5 wt.%- and 3 wt.%-doped sample are shown
in Fig. 8a and b, respectively. Response time is defined as
the time needed to reach 90% of the final steady value of the
sensor-resistance after test gas injection. Response times for
the doped films were estimated to be less than 2 s but recov-
ery time of the 5 wt.% WO3 -doped film was less (1.5 min) as
compared to the 3 wt.% WO3 -doped film (2.5 min). From all
these we can infer that the 5 wt.% WO3 -doped SnO2 film is
selective and sensitive to NO2 gas in comparison to other tested
gases.
The high response (∼33,400) towards NO2 gas at very low
temperature (150 ◦ C) can be explained on the basis of the change
in the energy barrier height due to doping of WO3 in the SnO2
film. Pure SnO2 and pure WO3 films show three activation ener-
gies, exhibiting three regions of conductance [21]. At lower
temperatures, the conductance of WO3 was almost four orders of
magnitude higher than that of SnO2 . Tungsten-doping increases
the intergrain energy barriers E as a function of temperature.
With an increase in loading concentration of the dopant the E
decreases. The decrease in conductance can be attributed to an
increase in the number of holes in the valence band injected by
the accepter dopants. The high energy barrier in case of pure
SnO2 and its dependence on temperature can explain its ability
to sense either reducing gases at high temperatures or NO2 gas
at low temperatures, while tungsten oxide, because of its low
energy barrier, is capable of sensing only oxidizing gases [22].
WO3 -doped SnO2 films extract the properties of both the mate-
rials, and this results in a decrease of response to other gases and
enhances the response to NO2 at comparatively low temperature
(150 ◦ C).
4. Conclusions
The response and selectivity of the SnO2 -based gas sensors
for NO2 gas have been improved significantly by adding an
appropriate quantity of WO3 dopant. It has been reported that the
dopant not only modifies the surface morphology but also low-
ers the operating temperature. Tungsten oxide has a low energy
barrier that makes it suitable to sense oxidizing gases at low
temperatures.
Acknowledgement
Authors are grateful to Department of Science, Delhi for the
financial support provided by them to carry out this research
work.
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Biographies
Jaswinder Kaur is a research fellow at the Thin Film Laboratory, Department
of Physics, Indian Institute of Technology Delhi, and New Delhi, India. She
obtained her BSc and MSc degrees in physics from University of Bhopal in
1999 and 2001, respectively. She completed her MTech (material science) in
2002. Her research interest includes sol–gel processing of nano-crystalline thin
films, gas sensing properties and study of interaction mechanism at gas–solid
interfaces.
Somnath C. Roy received his PhD degree in physics from Indian Institute of
Technology Delhi, India in 2005. His doctoral thesis was on electrical, optical
and gas sensing properties of sol–gel derived BST thin films. He received BSc
and MSc degrees in physics from Banaras Hindu University, Varanasi, India in
1997 and 1999, respectively. His areas of interest are dielectric, electrical and
gas sensing behaviour of oxide thin films. Currently, he is a lecturer in physics
at Amity University at Noida, Uttar Pradesh, India.
M.C. Bhatnagar is principal scientific officer at the Department of Physics, IIT
Delhi. He received his MSc (physics) and MTech (microwave engineering) from
University of Delhi and PhD in the field of ‘solar cells’ at IIT Delhi. His current
area of research includes development of humidity and gas sensors, associated
electronics and instrumentation, electronic noses, etc.