.

Sensors and Actuators B 60 1999 4956

www.elsevier.nlrlocatersensorb
Gas sensing properties of WO thick film for NO gas dependent on
3 2
process condition
Yong-Keun Chung
a
, Mi-Hyang Kim
b
, Woo-Sik Um
b,)
, Hee-Soo Lee
b
, Jun-Kwang Song
b
,
Sung-Churl Choi
a
, Kang-Myung Yi
c
, Myung-Jin Lee
c
, Kyung-Won Chung
c
a
Department of Inorganic Material Engineering, Hanyang Uniersity, Seoul 133-791, South Korea
b
Material Testing Team, Korea Testing Laboratory for Industrial Technology, Korea Academy Institute of Science and Technology, 222-13, Kuro 3-Dong,
Kuro-gu, Seoul 152-053, South Korea
c
Research and Deelopment Laboratory, Daejoo Fine Chemical, Shihwa IND, 1RA 110, 1236-10, Jung Wang Dong, Sihung, Kyunggi-Do, South Korea
Received 26 March 1999; received in revised form 29 March 1999; accepted 1 April 1999
Abstract
The thick film sensor of tungsten oxide for NO gas detection was fabricated by changing the process conditions, which were firing
2
temperature and annealing atmosphere. The origin of sensor property variation was interpreted by the characterization of crystallite size,
specific surface area and microstructure. The degree of oxygen deficiency in the WO sensor also affected sensor properties and the
3
optimum oxygen content of WO was necessary to get high sensitivity for NO . The WO thick film fired at 7008C and operated at
3 2 3
1008C showed excellent sensor properties, and its operation temperature is lower than that from other reports. q1999 Elsevier Science
S.A. All rights reserved.
Keywords: Thick film; Gas sensor; Tungsten oxide; NO gas; Screen printing method
2
1. Introduction
There are various types of sensor for detecting small
w x
concentrations of combustible or toxic gases in air 13 .
Among them, semiconductor gas sensors are particularly
interesting because of their structural simplicity and low
price. Numerous materials were reported to be usable as
semiconductor gas sensor, i.e., ZnO, SnO , WO , TiO ,
2 3 2
a-Fe O , etc. These candidates have non-stoichiometric
2 3
structures, so free electrons originating from oxygen va-
cancies contribute to electronic conductivity by following
w x
the equation 4 .
O bulk sV q2e
X
q1r2O gas 1 . . .
o o 2
SnO has been widely used as base material for detection
2
w x
of hazardous gases 5 , but has shortcomings, such as the
)
Corresponding author
lack of reproducibility, long term stability and selectivity
for specific gases, especially NO gas. Therefore, many
x
researchers have been studying materials to detect small
. w x
concentration ;ppm of NO gas 6,7 .
x
WO gas sensor was first reported by Shaver for detec-
3
w x
tion of H 8 . Recently, it has been reported that WO
2 3
materials have good selectivity for low concentration of
w x
NO gas 9 . But, most reports focus on the thin film type
x
w x
WO sensors 8,10,11 , and the study of thick film type by
3
screen printing method, especially process conditions, is
rare. In this report, thick film type WO sensors were
3
fabricated by screen printing method and the process con-
dition was changed to study the sensor property variation.
2. Experimental procedure
.
WO powder CERAC, 99.99% was ball-milled with
3
zirconia ball in ethyl alcohol for 24 h. After drying, the
powder was mixed with organic binder and solvent by a
three-roll mixer to make paste. The paste was printed on
0925-4005r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
. PII: S0925- 4005 99 00243- 9
( ) Y.-K. Chung et al.rSensors and Actuators B 60 1999 4956 50
.
the alumina substrate 4 mm=4 mm=0.4 mm patterned
by Au electrode and RuO heater on each side. The thick
2
films were then dried and fired at different temperatures
.
6008C, 7008C, 8008C for 1 h in air atmosphere. The
thickness of all thick films was about 30 mm. And the
thick films fired at 7008C was wire-bonded and then
heat-treated at the same temperature under different atmo-
sphere of ArrO .
2
The crystal phases and crystallite size were evaluated

by X-ray diffraction patterns XRD, Mac. Science

.
M18XHF-SRA . Crystallite size was calculated by Scher-
. . .
rers equation using the FWHM of 200 , 020 , and 002
w x .
planes 12 . BrunauerEmmettTeller BET method was

applied for specific surface area evaluation Quantachrome

.
Autosorb-1 . The microstructure of porous films was also

analyzed by using scanning electron microscope SEM,

.
S-2000, Hitachi .
The test box for NO monitoring is composed of two
2
parts; one is gas-in and out part and the other is circuit part
to check the change of resistance. Sensor was connected
with load resistance in series. DC 10 V was applied to the
circuit and sensor temperature was controlled using RuO
2
heater by applying DC voltage. Voltage value of load
resistance was read by voltmeter and was recorded by

computer. To know the sensitivity ratio of resistance in air

.
to that in gas variation dependent upon heater tempera-
ture, the operating temperature of gas sensor was changed
w x
from 708C to 3008C 5 .
3. Results and discussion
Fig. 1 shows XRD patterns of as-received and fired
thick films in the temperature range of 6008C8008C.
Crystal phases of WO thick films were triclinic, and the
3
appreciable difference in the orientation and phase be-
tween 6008C, 7008C, and 8008C-calcined samples was not
observed. Fig. 2 shows the surface microstructures of WO
3
thick films fired at 6008C, 7008C, and 8008C, respectively.
The size of grains and macro pores gradually increased
with increasing firing temperature. The firing at 8008C
induced the grain growth of the sensing layer from sub-mi-
cron to micron-order size and the color of the WO thick
3
.
film was also changed from yellow-green Fig. 2 a and
.. ..
b to dark green Fig. 2 c . Table 1 shows specific area
of WO powder and thick films with changing firing
3
condition. Specific surface area was decreased with in-
creasing firing temperature. Particularly, the large reduc-
tion of surface area on the thick films fired between 7008C
and 8008C agrees well with the results of SEM morphol-
ogy. However, three kinds of WO thick film have similar
3
crystallite size except for raw WO powders as shown in
3
Fig. 1. XRD patterns of as-received and WO thick films fired at various temperatures.
3
( ) Y.-K. Chung et al.rSensors and Actuators B 60 1999 4956 51
. . Fig. 2. SEM photographs of WO thick films fired at a 6008C, b
3
. 7008C, and c 8008C.
Table 2. This result was different from that of Tamaki et
w x
al. 12 that crystallite size increases with higher firing
Table 1
Specific surface area of WO powder and thick films under different
3
firing temperatures
Powder 6008C 7008C 8008C
2
. Specific surface area m rg 5.943 3.169 2.441 1.470
temperature. It is known that the only grain growth of
WO film occurs without increasing the crystalline size
3
inside a grain in various firing conditions after crystalline
size increases in firing process from raw powder in firing
process.
In order to check the sensitivity of WO sensors for the
3
.
concentration 100 ppm of NO test gas, WO sensors
2 3
were maintained at the various temperature from 708C to
3008C. As shown in Fig. 3, WO sensors responded to
3
turning-on and turning-off NO flow by the reversible
2
changes of electrical resistance. The resistance values in
air decreased with a rise in operating temperature. This is a
typical characteristic of ceramics. The large drop of initial
resistance values was observed between operating tempera-
tures of 708C and 1008C. After H O molecules adsorbed
2
on the surface of WO thick film are removed near 1008C,
3
electrons bonded with H O are re-introduced into the
2
conduction band and these free electrons lead to the in-
w x
crease of electrical conductivity 13 .
The resistance of WO sensors increased with turning
3
on NO flow below the operating temperature of 2508C.
2
But reverse tendency was observed above 2508C. After the
small increase of resistance in the moment of exposition to
NO , the resistance of WO thick film gradually decreased
2 3
to reach a lower steady state than the initial value. It is
considered that NO gas adsorbed on the WO surface
2 3

y
.
forms nitrito type adsorbates ONO , and dissociates into

y q
. w x
nitrosyl type adsorbates NO , NO 14 . That is, the
abnormal response of sensor for NO above 2508C might
2
originate from the superior number of NO
q
adsorbates
y
w x
than NO adsorbates 15 .
Fig. 4 illustrates NO gas sensitivities of WO sensors
2 3
fired in the temperature range of 6008C8008C. The sensi-
tivity of the sensor fired at 6008C is similar to that at
7008C. But the sensitivity of the sensor fired at 8008C was
very low. That is caused by the reduction of effective
surface area of the sensor for NO gas detection with
2
higher firing temperature as mentioned in the results of
BET and SEM. The maximum sensitivity of the sensors
for NO gas is shown at the operation temperature of
2
1008C. The increase of sensitivity until 1008C may origi-
Table 2
Average crystallite sizes of WO powder and thick films fired at various
3
temperatures
Powder 6008C 7008C 8008C
. Avg. crystallite size A 562 592 596 595
( ) Y.-K. Chung et al.rSensors and Actuators B 60 1999 4956 52
Fig. 3. Dependence of resistance of WO thick films upon firing and operating temperatures for NO gas.
3 2
( ) Y.-K. Chung et al.rSensors and Actuators B 60 1999 4956 53
. Fig. 3 continued .
Fig. 4. Sensitivity of WO thick films with changing the firing and operating temperature.
3
( ) Y.-K. Chung et al.rSensors and Actuators B 60 1999 4956 54
Fig. 5. Gas response and recovery characteristics of the WO thick films with firing condition.
3
nate from the removal of H O adsorbed on the surface of
2
WO thick film which makes the adsorption site for NO
3 2
gas. The increasing number of NO
q
adsorbates than NO
y
causes the continuous reduction of sensitivity above 1008C.
When the operating temperature was kept over 2508C, the
sensors had no sensitivity to NO gas. The response and
2
recovery speed for NO gas with firing conditions was
2
shown in Fig. 5. The sensing layer fired at 7008C indicates
the excellent response and recovery characteristics and the
saturated stable sensitivity.
Fig. 6 shows sensing characteristics of WO sensors
3
having different degree of oxygen deficiency for NO gas,
2
which were heat-treated at 7008C in various argon and
.
oxygen ratio to control the oxygen deficiency x value of
.
WO . In Fig. 6 a , initial resistance of gas sensor in-
3yx
creased up to 50% oxygen portion but decreased above
..
that point. Gas sensitivity Fig. 6 b had the same ten-
dency as initial resistance. When the heat-treatment atmo-
sphere was near 40%50% of oxygen portion in ArO
2
flow, WO sensors having optimum oxygen deficiency
3
show the best sensitivity for NO gas. This result suggests
2
that the sensitivity of WO gas sensor is dependent on its
3
resistance and oxygen deficiency. Based on this result of
our study, the authors intend to develop future studies to
investigate electronic properties of WO gas sensor and
3
calculate its number of mobile electrons.
4. Conclusions
WO sensor for NO gas detection was fabricated by
3 2
screen printing method. The firing of WO thick film was
3
performed at various firing temperatures and WO sensor
3
were heat-treated in various atmosphere of ArO flow.
2
The WO thick film fired at 7008C and operated at 1008C
3
showed excellent properties, which were fast response
time, saturated stable sensitivity and rapid recovery charac-
teristics to NO gas in air. This is because the effective
2
adsorption site of WO thick films to adsorb NO gas
3 2
increased from a micro-structural point of view. The maxi-
mum sensitivity of sensors to NO gas was observed when
2
the heat-treatment atmosphere was near to 40%50% of
oxygen portion in ArO flow. The control of oxygen
2
content of WO sensor was also important to improve the
3
sensitivity similar to microstructure control.
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Yong-Keun Chung received his MS degree in 1999, and is currently PhD
student at Hanyang University and research fellow in Korea Testing
. Laboratory KTL . His research has been mainly in the fields of elec-
tronic ceramics, especially gas sensor technology.
Woo-Sik Um received his PhD degree from KAIST in 1992, and the
subject of his thesis was superconductors. He is presently a senior
researcher at the KTL. His current interests are mainly powder synthesis
technology and electronic ceramics such as sensors and piezoelectric
transformers.
Hee-Soo Lee received his PhD degree on the subject of PZT thin film
from Hanyang University in 1998. He is working as a senior research
fellow at the KTL. His research interests include environmental ceramics.
Mi-Hyang Kim received her MS degree from Pusan University in 1995,
and she is working as a researcher at the KTL. Her current interests are
powder synthesis and organic chemistry.
Jun-Kwang Song received his MS degree from Yonsei University in 1995
and he is currently completing a PhD thesis on the subject of piezoelec-
tric transformers. He also works at KTL.
Sung-Churl Choi received his PhD degree in structural composite ceram-
ics from Stuttgart University in 1987. He was a research fellow at
Max-Plank Institute, Germany, from 1984 to 1987. He has been a
professor at Hanyang University, Korea. His research interests are in the
areas of structural ceramics, ceramic processing, and advanced compos-
ites.
Myung-Jin Lee received his MS degree from Jungang University in 1991.
He is a senior research fellow at research and development laboratory,
Daejoo Fine Chemical, Korea. His research interest is in the field of
powder preparation.
Kang-Myung Yi received his MS degree from Korea University in 1991.
He is a senior research fellow at research and development laboratory,
Daejoo Fine Chemical, Korea. His research interest is in the field of thick
film technology.
Kyung-Won Chung received his MS degree from Yonsei University in
1991 and he is in the course of getting his PhD degree. He is chief of
research and development, Daejoo Fine Chemical, Korea. Research inter-
ests of his lab are in the field of powder preparation and thick film
technology.