252

Sensors and Actuators B, 13-14 (1993) 252-255

Ejigh sensitivity and selectivity methane gas sensors doped with Rh a43a catalyst
Lkpwbmnt ofElectronics, KvLutgpwk National University, Taegu 702-701 (South Korea)

Duk-Dong Lee, Wan-Young Chung and Byung-Ki Sohn

Abstract
SnO*(Rh) thick-film devices for detecting methane gas selectively have been prepared
technique, and their characteristics have by the screen-printing

been investigated.The sensitivity of an SnOz thick film with added Rh to CH, (1000 ppm) is about 90% at an operating temperature of 400 C, which is higher than those of SnO, thick-film devices with added Pt or Pd.

1. Introduction
Until now, metal oxides such as SnO, and Fe,O, have been widely used as raw materials for hydrocarbon sensing devices [l-3]. The principal disadvantages of such devices include their relatively low selectivity and long-term drift. Methane is a principal component of liquefied natural gas, which is widely used in industry and the home as city gas. Since CI& is chemically stable, it is relatively difficult to detect with high sensitivity. Therefore, the development of sensors to detect CH, in air with high sensitivity is a matter of urgency. It has been reported that the gas selectivity and sensitivity of an SnO, sensor is enhanced by the addition of noble metals such as Pd and Pt, grain-size control of the raw powder [4] or mixing with an oxide additive. However, Rh has not often been applied as a catalyst compared with Pt and Pd [5]. In this study, Rh-doped SnO, fme powder was prepared by the coprecipitation method. Then a thick-film gas sensor made of this material was prepared by the screen-printing technique. The CI-I., sensing characteristics of this film have been investigated.

precipitation of an aqueous solution of S&l, or TiCl,, with or without SbCI, and an aqueous solution of RhC13~H20. The precipitate was dried at 110 C for 24 h, and then crushed with an agate mortar. The crushed powder was calcined at 520 C for 1 h in N, and mixed with Al,O, (10 wt.%). These final powder mixtures were mixed with deionized (DI) water or an aqueous solution of organic binder in order to obtain a thick-film paste which had enough viscosity for screen printing. These pastes were printed on the sensor surface hy a semi-automatic screen printer (de Haart SP-SA5, USA) with a 200 mesh stainless screen and dried in air for 20 h at 110 C after sufficient predrying at room temperature in air. The thick films were sintered at various temperatures for 2 h in N, ambient. A pair of electrodes was formed by d.c. sputtering of platinum (3ooo R). Figure 1 shows the structure of a thick-film-type sensor. The power consumption of the gas sensors is about 850 mW at 400 C.

3. Results and discussion 3.1. Characterimion of raw pow&r The method of impregnating raw powder with rhodium influences the distribution properties of the catalyst on the thick-film surface and the activity or gas sensitivities of the gas sensors to various gases. The effect of the synthesis method on the microstructure of SnO,(Rh) raw powder was observed by transmission electron microscopy (TEM; Hitachi H-600, Japan). As shown in Fig. 2, the grain size of the Rhdoped powder prepared by addition of RhCl, to precipitated SnO, was about 15 nm. On the other hand, the grain size

2. Experimental The SnO,(Rh) thick-film methane gas sensors doped with rhodium as a catalyst were prepared by the screenprinting technique. The raw materials, SnO, and TiO, were prepared by a precipitation method. Rh was added to the raw materials by two different methods. One method was the addition of Rh metal, which was decomposed from RhCl, *3H,O dissolved in n-butanol at 50 C. The other method was the simultaneous

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0 1993 - Elscvier Sequoia. All rights reserved

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Sensing

Material

f
Sensor Electrode

20 28

30
Meg.1

40

@I
Fig. 1. Overview of the sensor structure and A-A cross-sectional view.

Fig. 3. XRD patterns of (above) SnOz and (below) SnOz(Rh) powders.

(a)
100 SnOt(Rh)

Fig. 2. The SnO,(Rh) powder microstmcture typical method and (b) coprecipitation.

prepared

by (a) a
CH, CONCENTRATION (1000 ppm)

Fig. 4. Sensitivities to CH, of thick tibns of SnOZ(Rh), TiOz(Sb, Rb) and TiO,(Rh).

of the powder synthesized by simultaneous precipitation of the aqueous solution of SnCl., and RhCl,*xH,O was about 6 nm. The latter method, i.e. precipitation, is supposed to be advantageous over the former because it yields ultramicro sire grains that are homogeneously doped on a microscopic scale and keep a finely dispersed Rh state. Figure 3 shows XRD (Jeol JDX-8030, Japan) patterns of calcined SnO, and SnO,(Rh) powders. It seems that adding rhodium during precipitation suppressed the crystal growth of SnO,. 3.2. Gas-sensing characteristics The sensitivity of an SnO, thick tihn with &rely dispersed rhodium to methane was higher than that of SnO,(Pt) or SnO,(Pd) thick films at 400 C. Rhodium added to the SnOrbased thick film existed in the form of oxide at the surface, which was observed by ESCA data. Reduction of the thick film in a hydrogen ambient

at 500 C for 2 h improved the sensitivity to methane gas. Figure 4 shows the sensitivities to CH, of thick fihns of SnO,(Rh) (97.5:2.5 by weight), SnO,(Sb, Rh) (96.5:1:2.5 by weight) and TiO,(Rh) (97.52.5 by weight) at 400 C. The sensitivity to gases, S, is defined as S= (&-Rp$R.i,= W&

where R,, is the sensor resistance in fresh air and Rgm that in the presence of the gas. Figure 5 shows the sensitivities to CH., of thick films of SnOdPt) (99:l by weight), SnO,(Pd) (99:l by weight) and SnO,(Rh) (97.5:2.5 by weight) at 400 C. Figure 6 shows the sensitivities of the SnO,(Rh) sensor to 5000 ppm CO and CH, at various temperatures. As shown in this Figure, the SnO,(Rh) sensor exhibits a high selectivity to CH,, apart from CO above 400 C.

0.011
200 2000 CH, CONCENTRATION (ppm) 20000

Fig. 5. Sensitivities to CH, of thick lilms of SnO*(Pt), SnO*(Pd) and SnOZ(Rh)at 350 C. 35(30 2503
ml 503 WAVE NUMBERS(cm1

Fig. 7. IR spectra obtained after exposure of an SnO*(Rh) film surface to CH, at 200, 230 and 350 C, respectively (exposure time: 20 min).

following reactions are assumed: CIUgas) + 20,,, CH&,, CH3-Os, + H-O,, (1)

t 20,,, + 20- -

CO,(gas) + 3H-O,,, + 2e (2)

and

o.o:I300 350

400

450 ?C)

500

550

C&-O,,, + CH&,.t + 0- H,O(gas) + GK(gas) + 20,,, + e (3)

TEMPERATURE

Fig. 6. Sensitivities of SnOz(Rh) sensor to 5000 ppm CO and CB&at various temperatures.

Figure 7 shows IR spectra obtained after exposure of an SnO,(Rh) thin surface to methane at different specimen temperatures. As shown in thii Figure, the main products obtained from the reaction between CH, and SnO,(Rh) are CO, and H,O. Above 230 C, CO, and H,O appear as decomposition products (exposure time: 20 mm). So it is assumed that the following reactions will take place when CH., adsorbs on the surface of SnO,. The lattice oxygen, Olal, of SnO, can also be reactive with methane gas, at least in part due to its high concentration. However, in the presence of 02, as in the practical operating conditions of gas sensors, the adsorbed oxygens, O,- and O-, on the surface of SnOz are by far the more active forms. In this case, the

As shown in the above reactions between methane and the oxygens adsorbed either on the surface or from the lattice sites, oxygen vacancies or conduction electrons are produced when CO, and Hz0 gas molecules are produced. The sensor resistance was therefore decreased.

4. Conclusions Thick-film methane gas sensors doped with Rh as a catalyst were prepared by the screen-printing technique. The ultramicroparticle raw materials were synthesized by a precipitation method. The SnO,(Rh) thick film doped with 2.5 wt.% Rh, which was prepared by simultaneous precipitation of aqueous solution of SnCI, and RhC&-nH,O, exhibited good sensitivity to CH,. The gas sensitivities to 5000 ppm CH, in air of thick films of SnO,(Rh), SnO,(Pt), SnO,(Pd) were about 90,

2.55

75 and 70%, respectivelyat 400 C. Reduction of the SnO,(Rh) thick filmin H, ambient after heat treatment at 504 C improved the CI& sensitivity of the thick film. References
1 S. R. Morrison, Semiconductor gas sensors, Sensors and Actuators, 2 (1982) 329-341.

2 D.-D. Lee and W.-Y. Chung, Gas-sensing characteristics of

SnOl_, thin film with added Pt fabricated by the dipping method, Senws and Actuatom, 20 (1989) 301-305. 3 W.-Y. Chung and D.-D. Lee, Characteristics of a-FeO, thick 6hu gas sensors, llhln Solid Filmr, 200 (1991) 329-339. 4 S. Sakai, UK Parent No. 4 535315 (1985). 5 G. Munuera, A. R. GonzPez-Elipe, A. MuBoa,A. Fernandez, J. Soria, J. Coresa and J. Sanz, Mechanism of hydrogen gassensing at low temperatures using Rhniq systems, Sensors and Actuators, 18 (1989) 337-348.