Sensors and Actuators B 55 (1999) 166 – 169

Gas sensitivity of ZnO based thick film sensor to NH3 at room

temperature
G.S. Trivikrama Rao 1, D. Tarakarama Rao *
Inorganic Chemistry Di6ision, Indian Institute of Chemical Technology, Hyderabad 500 007, India

Received 20 April 1998; received in revised form 17 September 1998; accepted 21 September 1998

Abstract

Calcined powders of pure and doped ZnO have been prepared and characterized by XRD and scanning electron microscopy
(SEM). Employing these powders ZnO, Pd–ZnO, Fe– ZnO and Ru – ZnO thick film sensor elements have been prepared and
tested for specific sensitivity to ammonia gas in air at room temperature. Among all, Pd – ZnO showed high sensitivity to ammonia
in the range 50–90 ppm in air and showed a response time of  4 s at 30 ppm of ammonia gas. The observed specific sensitivity
to ammonia gas can be explained by a surface reaction process and a study of IR spectra obtained before and after exposing the
film to ammonia. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: ZnO thick film sensors; Specificity; Ammonia gas

1. Introduction obtained by controlling the operating temperature [6,7]

Applied chemical sensor research is focused on new
investigations to develop specific sensors. A device ca-
pable of mimicking the olfactory discrimination mecha-
nism would be useful to many industries, not only for
the detection of particular gases of interest, but also for
the evaluation of mixtures, for quality control in the
food and beverage industry, or environmental monitor-
ing [1] because users need to discriminate between the
pungent and minty odour. The mechanism may be
achieved by developing specific odour sensors like the
one investigated here and/or the sensors having differ-
ent specificity to different odours. Metal oxides such as
tin dioxide and zinc oxide fabricated either in the form
of thin films or as thick porous bodies, show an electri-
cal conductivity at a temperature of 300°C which is
very sensitive to the presence of trace amounts (ppm
levels) of reactive gases (hydrocarbons, hydrogen, car-
bon monoxide, methane, ammonia, oxides of sulphur
and nitrogen, chlorine, hydrogensulfide) in air.[2–5].
This phenomenon has been exploited for many years in
warning devices. A certain degree of selectivity can be
if the sensor is sensitive to many gases. A range of
materials has been investigated by Williams [8] who
concluded that most oxides respond to most gases and
a few materials showed selectivity to some gases. The
present study focused on developing selective gas sen-
sors based on pure and doped zinc oxide thick films. A
scheme of developing specific sensors for detecting
NH3, CO, H2, LPG, ethanol and acetone has been
undertaken and observed that pure and doped ZnO
thick film sensors are sensitive to NH3 selectively and
insensitive to other said species at room temperature in
the atmosphere. Incidentally, this is the first odour
sensor specific to NH3 at room temperature. In this
work, the preparation and characterisation of the base
sensor materials and the corresponding sensitivity, re-
sponse time etc. for the target gas has been discussed.
Also, the specific sensitivity to ammonia has been
explained.
2. Experimental

* Corresponding author. Tel.: +91-40-7170921; fax: + 91-40- Pure ZnO powder was prepared by reacting slowly
7173387. ZnCl2 with aqueous ammonium hydroxide solution.
1
Deceased The gel obtained in this way was filtered, washed and

0925-4005/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 ( 9 9 ) 0 0 0 4 9 - 0
 G.S.T. Rao, D. Tarakarama Rao / Sensors and Actuators B 55 (1999) 166–169 167

calcined at 600°C for 5 h. Doped ZnO powders were trations in the air.
obtained by impregnating 0.1wt% equivalent amount of
their aqueous chlorides in the calcined ZnO and the
resultant was filtered, washed and calcined at 600°C for 3. Results and discussion
2 h in air. All of these processed materials are charac-
terised by XRD, scanning electron microscopy (SEM)
3.1. Characterization of sensor materials
and IR spectra. The sensor elements are fabricated by
taking these powders separately and made into pastes
The method of impregnation of dopents in calcined
by adding suitable amount of distilled water and ap-
ZnO influences the distribution properties of the cata-
plied in between the gap of the pre-printed silver elec-
lyst on the thick film surface and the activity. The effect
trodes on alumina substrates and air dried, which
of the method of preparation on the microstructures of
resulted four thick film sensors, namely ZnO(S1), Pd–
ZnO (S2), Fe–ZnO(S3) and Ru – ZnO(S4). The sensor S1, S2, S3 and S4 raw powders are observed by SEM
characteristics such as gas sensitivity, response time etc. and as shown in Fig. 1(a–d). The observed particle size
has been evaluated at room temperature (309 2°C) and varies between 0.2 and 0.4 mm. Fig. 2 shows the XRD
environment, by changing the target gas (NH3) concen- pattern of S, S1, S2, S3 and S4. It seems that homoge-
nous crystal growth has occurred during the calcination

Fig. 1. Scanning electron micrographs of the samples (a) S1; (b) S2; (c) S3; and (d) S4.
168 G.S.T. Rao, D. Tarakarama Rao / Sensors and Actuators B 55 (1999) 166–169
Fig. 2. Diffraction patterns obtained by XRD for as prepared ZNO
and calcined samples of S1, S2, S3, and S4.
and the XRD data obtained was in good agreement
with the reported ASTM data.
3.2. Gas sensing characteristics
The sensitivity of ZnO with finely dispersed Palla-
dium (S2) to NH3 was higher than that of S1 or S3 or S4
for all the concentrations studied at room temperature.
Fig. 3 shows the sensitivity to NH3 of thick films of S1,
S2, S3 and S4. The sensitivity (Sg) to NH3 is defined as
Sg = 6a –6g/6a
where 6a is the sensor voltage output in air and 6g that
in the presence of the gas. The measuring circuit em-
ployed is as shown in Fig. 4. It has been noted that the
sensitivity increases with increasing concentrations of
NH3 in all these elements. Pd – ZnO (S2) has high
sensitivity when compared to others. Moreover, at these
operating conditions, all of the sensor elements are
insensitive to other test gases such as H2, CO, LPG,
ethanol, methanol and acetone.
Fig. 5 shows the response time of these elements to
30 ppm of NH3 in air and at room temperature. The
Pd–ZnO (S2) sensor element has a fast response time of
4 s and high sensitivity when compared to S1, S3 and
S4. The lack of a quick response to NH3 of S1, S3 and
S4 may be due to the low surface catalytic activity. The
response time of S2 for NH3 is repeatable for the
measured concentrations and the time drift is less than
0.5 mV h − 1.
Furthermore, it may be mentioned that the maxi-
mum deviation of the response potentials is less than
5% from batch to batch preparation of these materials.
The observed results are reproducible in a single batch
prepared sensor elements.
The observed specific sensitivity to NH3 can be ex-
plained by the surface reaction processes and the IR
spectra obtained (Fig. 6) before and after the exposure
of NH3. All of these elements adsorb H2O in the air
(3000–3660 cm − 1) which is clearly indicated in the IR
spectra along with starting material impurity like SO4
(2800–3000 cm − 1) and the residual ZnCl2 (1600–1800
cm − 1) which has not been oxidised to ZnO during
calcination. Upon exposure to NH3 a noticeable de-
crease in the hydroxyl bands of these sensors has been
observed which may be due to the surface reaction of
NH3 with physisorbed H2O. The resulted reaction
product (NH4OH) which is volatile in nature, may be
responsible in modulating the sensitivity. Further, the
negligible quantity of the surface reaction product and
its high volatility indirectly indicates the observed fast
response of these sensors to NH3 and quick recovery to
normal conditions. Moreover the observed insensitivity
to other interfering gases and vapours clearly indicates
the specificity to NH3. The observed changes in the
sensitivity in pure and doped sensor elements may be
attributed to the particle size variations in the calcined
powders. The Pd–ZnO which has shown high sensitiv-
ity to different NH3 concentrations has average low
particle size when compared to the other sensors as
evident in the SEM micrograph Fig. 1(b).
4. Conclusions
Thick film ammonia gas sensor elements with and
without dopents were prepared and characterised.
Among all of the devices tested, the Pd–ZnO exhibited
good sensitivity and response time to NH3 at room
temperature. The gas sensitivities to 30 ppm of NH3 of
ZnO(Pd), ZnO, ZnO(Fe) and ZnO(Ru) were 60, 35,
25 and 10%, respectively.
 G.S.T. Rao, D. Tarakarama Rao / Sensors and Actuators B 55 (1999) 166–169 169

Fig. 3. Sensitivity vs. ammonia gas concentration for S1, S2, S3, and S4.

Fig. 4. Employed voltage measuring circuit with source voltage, Vc;

Sensor, S; output voltage, Vo; and load resistance, RL.

Fig. 6. IR spectra for S1, S2, S3 and S4 before (top trace) and after
(bottom trace) exposure to ammonia gas.

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ammonia gas. 328 – 333.
[5] S. Gouverneur, C. Lucat, F. Minil, J.L. Aucouturier, IEE Trans.
Compon. Hybrids Manuf. Tech. 16 (1993) 505.
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