Sensors and Materials, Vol. 21, No.

5 (2009) 259–264
MYU Tokyo

S & M 0766

WO3 Crystals and Their NO2-Sensing Properties

Zhicong Meng*, Chizumi Kitagawa,
Akari Takahashi, Yu Okochi and Jun Tamaki

Department of Applied Chemistry, College of Life Science,

Ritsumeikan University, Kusatsu-shi, Shiga 525-8577, Japan

(Received April 6, 2009; accepted June 1, 2009)

Key words: WO3 sensor, semiconductor sensor, gas sensor, NO2 detection

WO3 film sensors with various crystalline morphologies have been investigated for
highly sensitive detection of dilute NO2. Four types of WO3 particles, spherical, disk,
cuboid, and hexagonal, were prepared by pyrolysis (spherical), precipitation method (disk),
and hydrothermal synthesis under different conditions (cuboid and hexagonal). WO3
film sensors were fabricated on Au comb-type microelectrodes by suspension dropping
using the various WO3 powders obtained, and their sensor properties to dilute NO2 were
investigated at 200°C. The cuboid WO3 film sensor showed the best response-recovery
property with 90% response and 90% recovery times of 1.3 and 0.9 min to 0.05 ppm
NO2 at 200°C, respectively. The hexagonal WO3 film sensor showed extremely high
sensitivity of 41.1 to 0.01 ppm NO2 at 200°C. The sensor performance suggested the
possibility of environmental monitoring of dilute NO2 using WO3 film sensors.

1. Introduction

It is well known that the detection and emission control of nitrogen oxides (NOx: NO
and NO2) are crucial points to reduce the noxious effects of occurences, such as acid rain,
photochemical smog, and production of ozone on the environment and human beings.
Semiconductor gas sensors based on metal oxides have been studied extensively,(1,2) and
WO3 has been demonstrated to be an excellent sensing material for NOx detection.(3–5)
It was found that the sensitivity to dilute NO2 can be much improved using a thin film
structure,(6–8) and WO3-based thin-film sensors are able to detect dilute NO2 below the
ppm level. In previous publications,(9,10) we reported on the thickness effect of WO3 thin-
film sensors, the performance of WO3 thick-film sensors and their sensing mechanisms.
In this study, WO3 film sensors, were constructed using four types of WO3 particles with
various crystalline morphologies, and their sensing properties in dilute NO2 detection
were investigated.

*Corresponding author: e-mail: mou@fc.ritsumei.ac.jp

259
260 Sensors and Materials, Vol. 21, No. 5 (2009)

2. Experiments

WO 3 particles exhibit various crystalline morphologies depending on their

preparation process. In this work, spherical, disk, cuboid, and hexagonal WO3 particles
were prepared and used to fabricate sensor elements. The sensing properties of the
various WO3 film sensors to dilute NO2 have been investigated.
Spherical WO3 particles were prepared by pyrolysis of (NH4)10W12O41·5H2O in air
at 850°C for 4 h. Disk WO3 particles were prepared by the precipitation method. An
aqueous solution of (NH4)10W12O41·5H2O was neutralized with nitric acid, and the
precipitate (H2WO4) obtained was filtrated, washed, and calcined at 400°C for 3 h in
air. Cuboid WO3 particles were prepared by hydrothermal synthesis. The H2WO4
precipitate obtained by precipitation, which is the same as that in the preparation of disk
WO3 particles, was placed in a pressure-resistant airtight container with ion-exchanged
water, and underwent hydrothermal synthesis at 160°C for 14 h. Hexagonal WO3
particles were also prepared by hydrothermal synthesis, but unlike in the preparation of
cuboid WO3 particles, the H2WO4 precipitate was hydrothermally synthesized with ion-
exchanged water and a surfactant, cetyltrimethylammonium bromide (CTAB), at 150°C
for 10 h. The product was found to be a mixture of cuboid and hexagonal WO3 particles.
However, a preparation method for pure hexagonal WO3 particles has not yet been
discovered.
The crystal structure and grain size of the various WO3 particles obtained were
evaluated by X-ray diffraction (XRD: Rigaku, Rint-2200) and field-emission scanning
electron microscopy (FE-SEM: Hitachi, S-4800), and the results are shown in Figs. 1 and

(a) (b)

(c) (d)

Fig. 1. SEM images of various WO3 particles: (a) spherical WO3, (b) disk WO3, (c) cuboid WO3,
and (d) hexagonal WO3.
Sensors and Materials, Vol. 21, No. 5 (2009) 261

2500 2500
triclinic (b)
(a)
(020)
2000 (002) 2000

Intensity [arb. unit]

Intensity [arb. unit]

(200) monoclinic
1500 (202) 1500

1000 1000

(112)
500 500

0 0
20 25 30 35 40 20 25 30 35 40
2 θ / deg (CuKα) 2 θ / deg (CuKα)

7000 2500

(c) (d)
6000
2000 hexagonal
Intensity [arb. unit]
Intensity [arb. unit]

5000 (200)
1500
4000

3000 1000 (001)

(201)
2000
500
1000

0 0
20 25 30 35 40 20 25 30 35 40
2 θ / deg (CuKα) 2 θ / deg (CuKα)

Fig. 2. XRD pattern of various WO3 particles: (a) spherical WO3, (b) disk WO3, (c) cuboid WO3,
and (d) hexagonal WO3.

2, respectively. The grains sizes of the spherical WO3 particles were estimated to be 70
–150 nm in diameter. Disk WO3 particles were estimated to be 50–200 nm in diameter
with a thickness of 20–30 nm. Cuboid WO3 particles were rectangular-shaped with a
side length of 50–200 nm, and hexagonal WO3 particles were hexagonal-disc-shaped
with a side length of 0.7–1 μm with a thickness of 20–30 nm. From XRD analysis,
the crystal structures of the spherical, disk, and cuboid WO3 powders were confirmed
to be triclinic mixed with a monoclinic crystal system, and the hexagonal WO3 was
crystallized in a hexagonal system.
WO3 films were fabricated by suspension dropping on a SiO2/Si substrate equipped
with Au comb-type microelectrodes (line width: 2 μm, distance between lines: 2 μm, and
electrode area: 0.5 × 0.5 mm2, without backside heater). A small amount of suspension,
which was obtained by mixing WO3 powder with ion-exchanged water, was dropped
onto the Au comb-type microelectrodes, dried, and calcined in air at 400°C for 3 h.
Figure 3 shows a schematic drawing of the sensor element. The film thickness could
be controlled in the range of 10–15 μm by changing the WO3 powder concentration in
262 Sensors and Materials, Vol. 21, No. 5 (2009)

SiO2/Si substrate (4×10 mm2) WO3 film

Au leads

Au comb-type microelectrodes

Fig. 3. Schematic drawing of WO3 film NO2 sensor.

suspension and the dropping amount of suspension. The surface morphology of the films
was confirmed by FE-SEM, which showed that the comb-type-microelectrode area was
completely covered by WO3 grains.
In the measurement of NO2-sensing properties, the WO3 film sensors were set into a
flow apparatus. The electrical resistances of the sensor elements were measured in dry
air (Ra) and in NO2-containing dry air (Rg) at 200°C. The sensitivity (S) was defined as
the ratio of Rg to Ra (S = Rg/Ra). The NO2 concentration was varied in the range of 0.01–0.5
ppm. A 5.37 ppm NO2 (N2 balance) tank and a pure O2 tank were employed to prepare
the dilute NO2 in the above concentration range, and the flow rate was maintained at 100
ml/min.

3. Results and Discussion

Figure 4 shows the sensitivities to dilute NO2 of four WO3 film sensors at 200°C as
a function of NO2 concentration, and Fig. 5 shows the response transient of the various
sensor elements to 0.05 ppm NO2 at 200°C. The sensing properties to dilute NO2 of
various WO3 film sensors are summarized in Table 1. The sensitivity of the spherical
WO3 film sensor to dilute NO2 was the lowest among the four sensors. It was predicted
that, owing to the low-density packing of spherical-shaped WO3 particles, diffusion of
oxygen into the WO3 film occurs easily, while adsorption of NO2 is suppressed, and
thus there is a decrease in sensitivity to NO2.(10) The sensitivities of the disk and cuboid
WO3 film sensors were similar. To 0.01 ppm NO2, the sensitivity was 6–10, while the
response-recovery characteristics showed that the cuboid WO3 film sensor has the best
recovery property among the four sensors. The 90% response and 90% recovery times
were 1.3 and 0.9 min to 0.05 ppm NO2 at 200°C, respectively. During the experiments,
the response-recovery characteristics of the sensor were almost unchanged to 0.01–0.5
ppm NO2. In the four sensors, the hexagonal WO3 sensor showed the highest sensitivity
to dilute NO2. The sensitivity to 0.01 ppm NO2 at 200°C was as high as 41.1. Although
the response-recovery of the hexagonal WO3 sensor was somewhat slower than those of
the other three sensors, the extremely high sensitivity to low-concentration NO2 is the
most attractive feature in applications for highly dilute NO2 detection. It is presumed
 Sensors and Materials, Vol. 21, No. 5 (2009) 263

4 4
10 Spehrical 10
Disk
Cuboid
Hexagonal

Sensor response (Rg/Ra)

103 103

2 2
10 10

101 101

100 100
−2 −1
10 10
NO2 Concentration [ppm]

Fig. 4. Sensitivities to NO2 of WO3 film sensors as a function of NO2 concentration (operating
temperature: 200°C).

0.30

0.25
(a) NO2: 0.05 ppm
6
(b) NO2: 0.05 ppm
Resistance [M ]

Resistance [M ]

0.20
4
0.15

0.10
2

0.05

0.00 0
0 2 4 6 8 10 0 2 4 6 8 10
Time [min] Time [min]

70 700

60
(c) NO2: 0.05 ppm 600
(d) NO2: 0.05 ppm

50 500
Resistance [M ]
Resistance [M ]

40 400

30 300

20 200

10 100

0 0
0 2 4 6 8 10 0 2 4 6 8
Time [min] Time [min]

Fig. 5. Response transients of various WO3 film sensors to 0.05 ppm NO2 at 200°C: (a) spherical
WO3, (b) disk WO3, (c) cuboid WO3, and (d) hexagonal WO3.

that the extremely high sensitivity of the hexagonal WO3 film sensor may be due to the
much higher adsorptivity of the film structure formed by the hexagonal WO3 particles,
or an extremely high NO2 adsorption face within the hexagonal WO3 particles. Further
studies on the sensing mechanism are in progress.
264 Sensors and Materials, Vol. 21, No. 5 (2009)

Table 1
NO2-sensing properties of various WO3 film sensors (operating temperature: 200°C)
WO3 particle Film thickness T90 of response T90 of recovery S0.01 ppm NO2 (Rg/Ra)
(μm) (min) (min)
Spherical 10.6 2.1 1.4 1.2
Disk 17.8 2.0 1.1 6.3
Cuboid 11.5 1.3 0.9 10.3
Hexagonal 14.4 2.4 1.4 41.1

4. Conclusions

Four types of WO3 particles, spherical, disk, cuboid, and hexagonal, were prepared
by pyrolysis, precipitation method, and hydrothermal synthesis under various conditions,
respectively. WO3 film sensors are fabricated on Au comb-type microelectrodes by
suspension dropping using the various WO3 powders obtained, and their sensor properties
to dilute NO2 from 0.01 to 0.5 ppm were investigated at 200°C. The cuboid WO3 film
sensor shows the best response-recovery property with 90% response and 90% recovery
times of 1.3 and 0.9 min to 0.05 ppm NO2 at 200°C, respectively. The hexagonal WO3
film sensor shows an extremely high sensitivity of 41.1 to 0.01 ppm NO2 at 200°C. The
sensor performance suggests possibilities for environmental monitoring and applications
requiring highly dilute NO2 detection.

Acknowledgment

This research was partially supported by the Japanese Ministry of Environment under
the project of “Promotion for Environmental Technology.” The subject of the research is
“Development of a compact and high-sensitivity semiconductor NO2 gas sensor setting
at road neighbor for environmental measurements.”

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