Sensors and Actuators B 119 (2006) 380–383

Fast response thin film SnO2 gas sensors

operating at room temperature
H.C. Wang, Y. Li ∗ , M.J. Yang
Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
Received 3 August 2005; received in revised form 19 December 2005; accepted 20 December 2005
Available online 20 January 2006

Abstract
SnO2 thin film gas sensors operating at room temperature were prepared with SnCl4 as the starting material. The gas sensing characteristics of
the sensors towards methyl alcohol vapor were investigated. The sensors exhibit ultra-fast and reversible electrical response (t90% ∼5 s for response
and ∼1 s for recovery) at room temperature. In addition, the electrical responses are reproducible during cycling tests. The particle size of the
hydrolyzed SnCl4 affects the sensitivity of the sensors, but does not have much effect on their response time. The sensors show different electrical
response in the detection of the vapors of methyl, ethyl, isopropyl and butyl alcohol at room temperature, which is proposed to be related to the
variation in the reducing ability of the alcohols with a different number of methyl groups.
© 2005 Elsevier B.V. All rights reserved.

Keywords: SnO2 ; Room temperature detection; Gas sensor; Methyl alcohol; Sensitivity

1. Introduction
Gas sensors have found wide applications in industrial pro-
duction, environmental monitoring and protection, etc. [1–5].
Among the sensors investigated and developed, SnO2 based
sensors received much attention since they can detect a wide
variety of gases with high sensitivity, good stability and also
low production cost [5–11]. However, like other semiconduc-
tor type gas sensors, SnO2 sensors should be operated at high
temperatures, which brings about much inconvenience for prac-
tical applications and sometimes is even unsafe for detecting
combustion gases [12–20]. In recent years, efforts have been
done to realize the room temperature detection by using nano-
sized SnO2 , applying the dopants in SnO2 films, etc. Law et al.
[18] developed individual single-crystalline SnO2 based photo-
chemical NO2 sensors that worked at room temperature. Tadeev
et al. [17] found that the addition of noble metals such as Pd
and Pt in SnO2 could decrease the working temperature of the
sensor and the detection of CO at near room temperature was
realized by optimizing the microstruture of the film and the con-
centration of the doping additives. Selim [19] fabricated a SnO2
thick film sensor doped with ZrO2 for the detection of H2 S at
room temperature, and Patel et al. [20] applied copper as a cat-
alytic layer over thin films of indium tin oxide (In2 O3 + SnO2 ) to
improve the sensitivity of the sensor to methanol at room temper-
ature. Srivastava et al. [21] found that annealing the SnO2 sensor
in oxygen plasma reduced its barrier height and improved the
sensitivity to enable the sensor to work at room temperature.
Wei et al. [16] also revealed that doping of even a very small
amount of single-wall carbon nanotubes (SWNTs) could effec-
tively improve the room temperature sensitivity of SnO2 sensors
towards NO2 . However, in general, the researches on the SnO2
sensors operating at room temperature are still quite limited and
much more work needs to be done to understand the sensing
mechanism and the relationship between the composition and
microstructure of SnO2 and its sensing properties at room tem-
perature. In this paper, we report our preliminary work on the
preparation of thin film SnO2 gas sensors featured with low tem-
perature annealing of hydrolyzed SnCl4 and on their gas sensing
characteristics at room temperature.
2. Experimental

All the chemicals used in the work are of analytical grade and
∗ Corresponding author. Tel.: +86 571 87952444; fax: +86 571 87952444. used as received. The precursor solution for the sensor fabrica-
E-mail address: liyang@zju.edu.cn (Y. Li). tion was obtained by the hydrolysis of SnCl4 in the existence of

0925-4005/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2005.12.037
 H.C. Wang et al. / Sensors and Actuators B 119 (2006) 380–383 381

urea. In a typical procedure, a flask containing 25 mL of an aque-

ous solution of SnCl4 (0.1 mol/L) was heated to 90◦ C. The urea
solution containing 1.2 g urea and 25 mL of deionized water was
slowly dropped into the SnCl4 solution with magnetic stirring
in 20 min. The obtained mixture was then heated for another
10 min, followed by ultrasonic vibration for 30 min. The colloid
particle size was controlled by tuning the concentration of urea
and reaction duration.
The as-prepared precursor solution was dip-coated onto a
clean glass ceramic substrate (4 mm × 6 mm × 0.5 mm) where
an interdigital array of gold electrodes had been previously
evaporated and photolithographically defined (the thickness and
width of tracks were 2 and 40 ␮m, respectively) by using an
automatic dip-coating machine. The as-coated sensor was then
heated at 150 ◦ C in air for 2 h to obtain the gas sensor.
The X-ray diffraction pattern of the SnO2 thin film so pre-
pared was obtained on a D/max-rA X-ray diffractometer with Fig. 1. X-ray diffraction pattern of a SnO2 film annealed at 150 ◦ C.
CuK␣ radiation at room temperature. The 2θ scanning range was
set from 10◦ to 80◦ . The particle size of the hydrolyzed SnCl4
was determined on a 90 Plus Particle Size Analyzer (Brookhaven
Instrument Corporation). The gas sensing characteristics of the
thin film SnO2 sensor were investigated by recording online the
electrical response of the sensor to periodical changes between
dry air (dried with silica gel) and saturated vapors of alcohols
(methyl, ethyl, isopropyl and butyl alcohol) using a home-made
electric circuit at room temperature. The electrical voltage of
the sensor was collected by a PS-2104 AD/DA data-acquisition
card and input into a computer. The dry air was obtained in a
bottle containing silica gel, and the saturated gas vapors were
obtained in a bottle containing the liquids of the tested alcohols
where gas–liquid equilibrium was regarded to be achieved after
standing for a long time.

3. Results and discussions

The preparation of SnO2 gas sensors usually involves anneal-

ing at a high temperature of 400–950 ◦ C [4–5,7–11,16]. In this Fig. 2. Electrical responses of four sensors to the saturated vapor of methyl
alcohol at room temperature.
paper, the fabrication of the sensitive film is featured with the
annealing of the SnCl4 hydrolyzed with urea at a temperature
the sensor resistance in the gas and Rgas is that in dry air. The
as low as only 150 ◦ C. The XRD pattern of the SnO2 film so
responses of sensors A, B, C and D are thus calculated to be
prepared is presented in Fig. 1. It can be seen that the annealed
241, 318, 363 and 326, respectively. In addition, the electrical
film shows a strong peak corresponding to (1 0 1) plane with
response is fast and highly reversible for both the sensing and
narrow width, which was attributed to a polycrystalline phase
the recovery process irrespective of the particle size. Table 1
with preferred orientation structure.
summarizes the 90% time (t90% ) for the response and recovery
It is known that the microstructure of the sensing film, includ-
of the four sensors. It reveals that the sensors exhibit a very
ing the grain size, affects its sensing properties. In our work,
quick response and t90% is no longer than 6 s except Sensor C.
four sensors A, B, C and D were prepared from the precursor
As known the gas sensor operating at room temperature rarely
solutions with the colloid particle size of 6.0, 30.3, 49.2 and
319.9 nm, respectively, and their electrical response to dry air
Table 1
and the saturated vapor of methyl alcohol at room temperature The response and recovery time of the SnO2 sensors for the detection of the
are shown in Fig. 2. Currently most of the semiconductor gas saturated vapor of methyl alcohol at room temperature
sensors based on SnO2 , ZnO, Fe2 O3 , etc. exhibit gas sensitiv-
Sample Number Response time (t90% ; s) Recovery time (t90% ; s)
ity only when heated to several hundred degrees. However, it
can be seen in Fig. 2 that all the four SnO2 sensors so prepared Sensor A 5 <1
exhibit a large change in the electrical signal upon exposure to Sensor B <4 <1
Sensor C 34 <1
the saturated vapor of methyl alcohol at room temperature. The Sensor D 6 <1
response magnitude S is defined as S = (Rair /Rgas ), where Rair is
382 H.C. Wang et al. / Sensors and Actuators B 119 (2006) 380–383

Fig. 3. Electrical responses of the SnO2 sensor to periodical changes between Fig. 4. Electrical responses of the SnO2 sensor to the saturated vapors of methyl,
dry air and saturated vapor of methyl alcohol at room temperature. ethyl, isopropyl and butyl alcohol at room temperature.

The SnO2 gas sensor is known to show poor selectivity. Here

exhibits reversible response since the thermal energy is usually
the responses of the new SnO2 sensor to the vapors of four alco-
lower than the activation energy for desorption. This leads to
hols with a different number of methyl groups were investigated.
a long recovery time, and UV illumination and application of
Fig. 4 shows the electrical response of sensor B exposed to dry
gate potential were used to refresh the sensors [22]. However,
air and the saturated vapors of four alcohols including methyl,
in the present work, it was found that all the four SnO2 sensors
ethyl, isopropyl and butyl alcohol. It can be seen that the sen-
showed an ultra-fast reversible response at room temperature
sor exhibited quick response and recovery when exposed to the
with a recovery time t90% shorter than 1 s. The results indicate
vapor of methyl alcohol with a response of S = 318. Its response
that the particle size of the hydrolyzed SnCl4 can affect the sen-
to ethyl alcohol was a little bit slower but the recovery was still
sitivity, but does not have a great effect on the response time
quite fast, and the response decreased to S = 193. Furthermore,
of the sensors, and more work has to be done to understand
the sensor exhibited a quite small response of S = 3 to isopropyl
the reasons. It is worth noting that the ultra-fast and reversible
alcohol and was completely insensitive to n-butyl alcohol. The
response at room temperature, which is of prime importance
results suggest the sensor exhibits selectivity in the detection of
for the development of advanced gas sensors, has been real-
alcohols. Forming composites with carbon nanotubes or organic
ized in the sensors prepared by the very simple method featured
gas sensitive materials may be helpful for further improving the
with hydrolysis and low temperature annealing of SnCl4 . In this
selectivity of the SnO2 sensor operating at room temperature.
report, the sensors were used to detect the saturated vapor of
The different sensing properties may be related to the variation
methyl alcohol of high concentration, and it was found that the
in the reducing properties of the alcohols, as proposed by Gong
sensitivity decreased quickly with decreasing the concentration,
et al. [23]. More work has to be done to understand the reasons
and the sensor exhibited only a response of S = 3 for a methyl
that the SnO2 sensors exhibit very short response and recovery
alcohol vapor concentration of 40000 ppm. More efforts need to
time, reversible and reproducible response for the detection of
be done to increase the sensitivity of the SnO2 based sensor in the
methyl alcohol vapors at room temperature.
detection of low concentration vapor, including doping it with
noble metal ions, forming composites with carbon nanotubes
and conducting polymer gas sensitive materials, etc. 4. Conclusions
Selim [19] reported that a ZrO2 doped SnO2 thin film showed
high sensitivity and fast response in detecting H2 S at room tem- Thin film SnO2 gas sensors can be prepared by the hydrolysis
perature, but the response was not reproducible. Tadeev et al. and low temperature annealing of SnCl4 . The sensor is featured
[17] also found that the maximum sensitivity of a Pd-doped with fast, reversible and reproducible response to methyl alcohol
SnO2 film for the detection of CO was observed at room temper- vapors at room temperature.
ature, but the sensitivity strongly decreased after the first cycle.
Fig. 3 shows the electrical response of sensor B to periodical
changes from dry air to the saturated vapor of methyl alcohol Acknowledgements
at room temperature. It can be seen that the sensing properties,
including the sensitivity, the response and recovery time, do not This work is financially supported by the National Natural
change during ten cycles of tests. The results indicate that the Science Foundation of China (Contract no. 50403020) and Zhe-
sensor exhibit reproducible responses for the detection of methyl jiang Provincial Natural Science Foundation of China (Grant no.
alcohol vapor. M203093).
 H.C. Wang et al. / Sensors and Actuators B 119 (2006) 380–383
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Biographies
Hui-cai Wang is now a PhD student in the department of polymer science and
engineering, Zhejiang University, China. His research interests are polymer and
composite materials for gas sensors.
Yang Li received his PhD degree in polymer chemistry and physics from Zhe-
jiang University in 2000. He has been working in Department of Polymer Science
and Engineering, Zhejiang University since 2000 and was appointed associate
professor in polymer science in 2002. His research interests include polymer
materials and organic/inorganic composites for chemical sensors.
Mu-jie Yang graduated from Zhongshan University, China in 1963. She has been
working in Zhejiang University since 1963. She was promoted to full professor
in polymer science in 1992. Her research interests are functional polymers with
optical and electrical characteristics.