Sensors and Actuators B 64 2000.

3136
www.elsevier.nlrlocatersensorb

Fabrication and characterization of micro-gas sensor for nitrogen oxides

gas detection
Dae-Sik Lee a,) , Jun-Woo Lim a , Sang-Mun Lee a , Jeung-Soo Huh b,1, Duk-Dong Lee a
a

School of Electronic and Electrical Engineering, Kyungpook National Uniersity, Taegu 702-701, South Korea
b
Department of Metallugical Engineering, Kyungpook National Uniersity, Taegu 702-701, South Korea

Abstract
WO 3-based thin film micro-gas sensor was fabricated and the NO x gas sensing as well as electrical properties have been investigated.
To obtain the optimal heat distribution, the structure of micro-hot plate was designed from the result of finite element simulation and was
prepared by backside etching with KOH solution.
The micro-hot plate was made out of NrOrN diaphragm with the thickness of 0.6 nm and area of 1.5 = 1.5 mm2. The power
consumption to maintain the device temperature of 3008C was about 60 mW. WO 3 thin film was thermally evaporated on micro-diaphragm. The film exhibited a fast response to NO 2 gas and the relationship between sensitivity and NO 2 concentration showed good
linearity in the gas concentration range of 030 ppm NO 2 . The sensitivity of micro-gas sensor to NO x was correlated with the
microstructure of the thin film. q 2000 Elsevier Science S.A. All rights reserved.
Keywords: Nitrogen oxide; Micro-gas sensor; Tungsten trioxide; Thermal evaporation

1. Introduction
Nitrogen oxides NO and NO 2 : NO x ., released from
combustion facility and automobiles, are known to be
extremely harmful to human body and also a main cause
of air pollution w1x. So far, several oxide semiconductors
have been employed for the detection of NO x w24x. WO 3
is considered as one of the best candidates for NO x-sensing
materials w5x. It has been reported that the sensitivity of
WO 3 sensor to NO x is enhanced by adding metals such as
Au, Ti, Al, or Pt w6,7x, and it is usually made up of thick
film or thin film on alumina or silicon substrate by means
of screen-printing, sputtering, or evaporation method w8 9x.
The current trend is directed towards fabrication of
sensors by the use of micro-technology. The micro-type
sensor has many advantages over bulky sensor, i.e., high
productivity, possibility of intellectualization, low power

consumption and low cost etc. We fabricated the WO 3based micro-NO x gas sensor on the micro-diaphragm obtained by photolithography and micro-machining process
on the purpose of high productivity and low power consumption. The microstructure of WO 3-based thin film has

)
Corresponding author. Tel.: q82-53-939-1074; fax: q82-53-9391073.
E-mail addresses: ddlee@ee.kyungpook.ac.kr D.-S. Lee .,
jshuh@bh.kyungpook.ac.kr J.-S. Huh..
1
Tel.: q82-53-950-5562.

0925-4005r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 9 9 . 0 0 4 7 9 - 7

Fig. 1. Schematic diagram of the micro-gas sensor.

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D.-S. Lee et al.r Sensors and Actuators B 64 (2000) 3136

Fig. 2. Photographs of fabricated micro-gas sensor: a. front view, b.

back view.

been submitted to analysis by SEM, XRD, XPS, AES and

AFM. We also investigated the NO 2-sensing and electrical
properties of WO 3-based thin film on diaphragm.

Fig. 3. SEM photograph of the surface of WO 3 thin film at different

temperatures: a. 500 , b. 600 , c. 800 , and d. 1000 8C.

D.-S. Lee et al.r Sensors and Actuators B 64 (2000) 3136

2. Experimental
Fig. 1 shows the cross-sectional view of the micro-gas
sensor structure. As shown in Fig. 1, the micro-NOx sensor
is composed of WO 3-sensing film, Pt heater, and electrodes on a stress-free Si 3 N4rSiO 2rSi 3 N4 diaphragm.
The structure of micro-gas sensor was designed according to the results of thermal analysis. To get the optimal

33

heat distribution on the micro-hot plate, finite-element

simulation has been employed. The micro-sensor has characteristic dimensions such as sensing area of 0.24 = 0.24
mm2 , diaphragm area of 1.5 = 1.5 mm2 for Pt heater and
electrode, and total area of 3.78 = 3.78 mm2 after backside
etching of Si. For micro-NOx gas sensor fabrication, three
masks were used; the first one for the window opening to
etch the backside of Si, the second one for the Pt electrode

Fig. 4. AFM surface morphology of WO 3 thin film: a. room temperature, b. 600 .

D.-S. Lee et al.r Sensors and Actuators B 64 (2000) 3136

34

Fig. 5. XRD spectra of WO 3 thin film for different annealing temperature WO 3 : triclinic B., tetragonal '., Pt v ..

and surrounding heater on the diaphragm, and the third for

NO x-sensing layer. Photolithography was employed for
patterning, especially lift-off process for sensing materials.
The top view of the fabricated micro-gas sensor is shown
in Fig. 2.
A WO 3 film as base-sensing material was deposited by
thermal evaporation method for the fabrication of high
porosity film. WO 3 powder of 1 g Junsei. was pressed
into a pellet and then evaporated up to thickness of 12,000
Then sputtering of Ti 1 vol.%., Au 1 vol.%., Pt 1
A.
vol.%., or evaporation of Al 1 vol.%. was performed to
investigate the effect of metals addition. The deposited
thin film was annealed at 6008C for 2 h in air. After wire
bonding for pad and aging, the sensing properties of
micro-gas sensor was tested in the gas batch system with
NO 2 and air as a balance gas. The microstructure of
sensing-film has been investigated by SEM, XRD, XPS,
AES and AFM. We used the voltage detecting method for
calculating the sensitivity of the sensor w10x. The sensitivity is defined as R gasrR air , where R gas and R air are the
electric resistance in the NO 2 gas and that in clean air,
respectively.

abruptly decreased to about 0.1 mm. In case of annealing

over 8008C for 2 h, particle migration and nucleation
appear and especially, for the film annealed at 10008C, the
connection of particle is obviously observed.
Fig. 4 shows the surface morphology of WO 3 thin film
as-deposited at room temperature and annealed at 6008C
by AFM. The as-deposited film shows rougher surface
morphology. But WO 3 molecules diffuse to smooth surface of low surface energy state after annealing for 2 h at
6008C in air. We also confirmed that the annealed WO 3
thin film on diaphragm is appears to be nearly stoichiometric considering W4f 7r2 binding energy peak of 35.2 eV by
XPS.

3. Results and discussion

Fig. 3 shows SEM photographs of the surface of WO 3
thin film obtained at different annealing temperatures. As
shown in Fig. 3, the particles of WO 3 thin film annealed at
5008C for 1 h are irregular hexahedron-shaped and the
average grain size is about 2 mm in diameter as shown in
Fig. 4a.. The particle size of the film annealed at 6008C

Fig. 6. The relation of heater temperature and power consumption of the

sensor measured and simulated.

D.-S. Lee et al.r Sensors and Actuators B 64 (2000) 3136

35

Fig. 9. Time response of WO 3 thin film at 10 ppm NO 2 ambient.

Fig. 7. Sensitivity to 10 ppm NO 2 of pure and metal-doped WO 3 from
250 to 350 .

Fig. 5 shows the XRD patterns of WO 3 thin film for

different annealing temperatures. As shown in Fig. 5, in
as-deposited film, the peaks corresponding to Pt v . appear clearly. From 500 to 8008C annealed films, triclinic
phase B. of WO 3 is observed. The phase is transformed
to tetragonal phase '. over 8008C. By employing the
Scherrers formula w11x, the calculated grain sizes of thin
film annealed at 500, 600, 800, and 10008C were, respectively, 20, 22, 34, and 47 mm. In our experiment, the
optimal annealing temperature of WO 3 thin film for NO x
detection was about 6008C, considering the sensitivity.
This corresponds to the results of Tamaki and Yamazoe s
w12x experiment on the grain size effects in WO 3 for NO x
detection.
Fig. 6 shows the correlation between the heater temperature and power consumption of the micro-sensor that is
measured and simulated by finite element method for the
diaphragm with Pt heater. The diaphragm temperature is
calculated using the equations R s R 0 1 q a T ., where a
is known as 0.0035 empirically. Over the diaphragm tem-

perature of 1008C, it shows some deviation between simulated and measured temperature. This is due to the fact that
the effect of thermal loss through bonding wire line was
not considered for simplicity. It shows that power consumption to maintain diaphragm temperature at 3008C is
only about 60 mW.
Fig. 7 shows the NO 2-sensing property of five different
sensors for different diaphragm temperatures from 250 to
3508C in NO 2 10 ppm ambient. It shows that the optimal
operating temperature of WO 3-type NO 2 sensor is about
3008C, considering sensitivity to NO 2 . The pure WO 3
sensor exhibits higher sensitivity of about 3.3 to NO x at
3008C than those of metal-doped WO 3 thin film sensors.
metal layer Pt, Ti, Al or Au. to
The addition of 100A
WO 3 thin film has not improved NO 2 detection.
Fig. 8 shows the NO 2 gas-sensing properties of WO 3based micro-gas sensor when the gas concentration is
changed from fresh air to 30 ppm NO 2 ambient at the
operating temperature of 3008C. The micro-gas sensor with
pure WO 3 thin film shows good linearity of sensitivity to
NO 2 gas concentration and high sensitivity of about 9 to
30 ppm NO 2 gas at 3008C.
Time response of micro-gas NO 2 sensor in 10 ppm
NO 2 at 3008C is shown in Fig. 9. Resistance changes from
248 to 635 k V, which resulted in a sensitivity of 2.6. It
takes 12 min for the sensor to reach 90% of the response
and over 5 min to recover the original value. Therefore, it
may be used for a portable NO x detector with small power
consumption.

4. Conclusion

Fig. 8. Sensitivity of micro-gas NO x sensor for concentration change of

NO 2 gas.

A WO 3 thin film micro-gas sensor has been fabricated

using photolithography and bulk micro-machining technique. Micro-hot plate using stress-free NrOrN film is
designed from the finite-element simulation and fabricated
by backside etching with KOH solution and RIE etcher.
The power consumption was 60 mW at the optimal operating temperature of 3008C. After annealing at 6008C for

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D.-S. Lee et al.r Sensors and Actuators B 64 (2000) 3136

2 h, WO 3 thin film on diaphragm showed the small

particle size of about 100 nm, small grain size of 20 nm,
and smooth surface morphology with exact stoichiometry.
WO 3 thin film shows a good sensitivity of about 9 to 30
ppm NO 2 , fast response time of 12 min and good
linearity to NO x gas concentration at operating temperature of 3008C. Therefore, the micro-NO x gas sensor can be
applied for portable NO 2 gas detector for environmental
monitoring.

References
w1x N.O. Korolkoff, Survey of toxic gas sensors and monitoring systems, Solid State Technology 32 1989. 4964.
w2x G. Sberveglieri, Radio frequency magnetron sputtering growth and
characterization of ITO thin films for NO 2 gas sensors, Sensors and
Actuators, B: Chemical 15 1988. 235242.
w3x K. Satake, T. Takeuchi, Titania NO x sensors for exhaust monitoring,
Sensors and Actuators, B: Chemical 20 1994. 111117.

w4x S. Kudo, M. Ippommatsu, NO x sensor using YBa 2 Cu 3 O 7y d thin

films, Sensors and Actuators, B: Chemical 23 1995. 219222.
w5x M. Akiyama, N. Yamazoe, Tungsten oxide-based semiconductor
sensor highly sensitive to NO and NO 2 , Chemistry Letters 1991.
16111614.
w6x M. Akiyama, N. Yamazoe, Tungsten oxide-based semiconductor
sensor for detection of nitrogen oxide in combustion exhaust, Sensors and Actuators, B: Chemical 1314 1993. 619620.
w7x P. Nelli, G. Sberveglieri, Sub-ppm NO 2 sensors based on nanosized
tin films of titanium-tungsten oxides, Sensors and Actuators, B:
Chemical 31 1996. 8992.
w8x S. Yan, L. Young, Pulsed laser deposition of WO 3 base NO 2 gas
sensor, Technical Digest 7th IMCS, Beijing, China, July 2629
1998. 562564.
w9x C. Cantalini, M. Passacantando, NO 2 sensitivity of WO 3 thin film
obtained by high vacuum thermal evaporation, Sensors and Actuators, B: Chemical 31 1996. 8187.
w10x T. Seiyama, Gas detection by activated semiconductor sensor, Denki
Kagaku 40 3. 1972. 244249.
w11x B.D. Cullity, in: Elements X-Ray Diffraction, 1990, p. 127.
w12x J. Tamaki, N. Yamazoe, Grain-size effects in tungsten oxide-based
sensor for nitrogen oxides, Journal of the Electrochemical Society
141 8. 1994. 22072210.