Sensors and Actuators B 87 (2002) 207210

Short communication

Highly sensitive mixed oxide sensors for the detection of ethanol

B.P.J. de Lacy Costello, R.J. Ewen, N. Guernion, N.M. Ratcliffe*
Centre for Research in Analytical, Materials and Sensor Sciences, Faculty of Applied Sciences, University of the West of England, Frenchay Campus, Coldharbour Lane, Bristol BS16 1QY, UK Received 28 January 2002; received in revised form 10 May 2002; accepted 16 May 2002

Abstract Sensors consisting of mixtures of tin dioxide and zinc oxide powders in a range of proportions were constructed. Each mixture was applied to an electrode-bearing alumina substrate either as a paste, or by screen printing. The responses of these sensors, and of three commerciallyavailable Figaro sensors, to ethanol vapour in the 11000 parts-per-billion (ppb) range were measured. At 100 ppb of ethanol vapour, the most sensitive paste sensor (25% SnO2/75% ZnO) exhibited a response that was more than twice that of the screen-printed sensors, and almost 60 times greater than that of the most sensitive Figaro sensor (TGS822). # 2002 Published by Elsevier Science B.V.
Keywords: Tin dioxide; Zinc oxide; Mixed oxide sensor; Ethanol sensor; Electronic nose

1. Introduction The use of tin oxide as the basis of gas sensitive lms has been extensively reported. Both thin [1] and thick [2] lm sensors made using a variety of techniques have been studied for uses in the detection of a large range of organic and inorganic vapours. Sensors based on these materials usually possess little selectivity to any one vapour but exhibit good sensitivity to a broad range of vapours. Therefore, the sensors are commonly doped with catalytic metals such as platinum [3] or metal oxides such as copper oxide [4] to impart selectivity, increase sensitivity and enhance stability. Sensors based on zinc oxide are not as commonly reported in the literature, but thin lms have been utilised for the detection of carbon monoxide, hydrogen and methane [5]. Thin lm zinc oxide sensors doped with aluminium have also been utilised for the detection of trimethylamine [6]. Sensors based on composites of zinc oxide and tin oxide have been reported [79]. In early reports the sintering process was described as leading to the formation of ZnSnO3 [7] and Zn2SnO4 [8] intermediates and these were found to have some selectivity to ethanol vapour and NO2 gas respectively. However, the control of sintering temperatures has led to composites without intermediate compounds [9].
Corresponding author. Tel.: 44-117-344-2501; fax: 44-117-344-2904. E-mail address: norman.ratcliffe@uwc.ac.uk (N.M. Ratcliffe). 0925-4005/02/$ see front matter # 2002 Published by Elsevier Science B.V. PII: S 0 9 2 5 - 4 0 0 5 ( 0 2 ) 0 0 2 2 0 - 4
*

The enhanced sensing characteristics of these composites were postulated to be due to hetero-contacts formed on sintering the materials and also on changes in the microstructure making the materials more porous. A range of composite materials (290 mol.% ZnO) have been shown to have different sensing characteristics to CO gas when compared to the pure materials. The temperature at which maximum sensitivity to CO was observed was dependent upon the composition. The maximum sensitivities of these sensors were commonly in the tens of ppm (v/v) range. Here, we report the development of sensors that are sensitive to ethanol in the 11000 parts-per-billion (ppb) (v/v) range. Both screenprinted and thick-lm paste sensors are described.

2. Experimental 2.1. Screen-printed sensors Zinc oxide powder (AnalaR grade, 99.5%, BDH/Merck Ltd., Lutterworth, Leicestershire, UK) and tin dioxide powder (99.999%, Janssen Chimica, Hyde, Cheshire, UK) were used in the production of the sensors. A mixture of 0.5 g of each of the oxides was ground using an agate pestle and mortar. Cellulose acetate was added to act as a binder, then the grinding of the ingredients in the pestle and mortar was continued to produce a thick, coherent paste.

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Alumina substrates were prepared, each consisting of a pair of screen-printed interdigitated platinum electrodes (three pairs of interpenetrating bars, electrode gap 200 mm) on one side of the substrate and a screen-printed resistance heater on the reverse. The zinc oxide/tin dioxide/ cellulose acetate paste was applied to an appropriately masked mesh screen (mesh size 3:25 104 m) and was then printed on to the interdigitated electrodes. The resulting lms were then dried for 1 h at 100 8C and then subsequently at 350 8C for 24 h prior to use. The average dry lm thickness was 3 mm, measured using scanning electron microscopy (SEM). 2.2. Thick-film paste sensors Uncoated substrates upon which the paste sensors were prepared were obtained from Capteur Sensors and Analysers Ltd. (Abingdon, Oxon, UK). These consisted of a 3 mm alumina square with interdigitated gold electrodes (two pairs of interpenetrating bars, electrode gap 200 mm) on one side and a platinum heater on the reverse. The substrates were mounted on eight-pin dual-in-line headers before use. Zinc oxide powder (AnalaR grade, 99.5%, BDH/Merck Ltd., Lutterworth, Leicestershire, UK) and tin dioxide powder (99.9%, SigmaAldrich Chemical Co., Gillingham, UK) were used in the production of the sensors. Pastes incorporating mass percentage ratios of 100:0, 75:25, 50:50, 25:75 and 0:100 tin dioxide:zinc oxide, respectively, were produced in the following way: the oxide or oxide mixture was (100 mg) ground in an agate pestle and mortar with a few drops (ca. 0.15 ml) of distilled water for 15 min to produce a thick paste. The aqueous paste (3 mg) was applied to the substrate surface using a micro-spatula. The paste was allowed to dry for 24 h at 25 8C and then heated to 350 8C for 24 h prior to testing. The average dry lm thickness was 50 mm, measured using SEM. 2.3. Commercially-available sensors Three Figaro gas sensors, types TGS 800, TGS 822 and TGS 842 (manufactured by Figaro Engineering and obtained from Envin Scientic Products Ltd., Aylburton, Glos., UK) were selected. The sensors were heated to 350 8C by applying 5 V to the heating lament and were left in clean dry air to equilibrate for 24 h prior to testing. 2.4. Apparatus for sensor testing The sensors were tested in an in-house designed injection test rig. The test chamber consisted of an aluminium baseplate which was covered by a detachable dome shaped glass vessel (volume 13.75 l) which was sealed to the base-plate via a viton gasket. The top of the dome was tted with a port containing a silicone rubber septum (Fisons Scientic Equipment, Loughborough, Leicestershire, UK) through which test vapour could be injected. Zero-insertion-force

sockets mounted on the base-plate permitted the easy tting and removal of the sensors. The base-plate also contained two tubular feed-throughs (one inlet, one outlet), connected through electromagnetically operated on/off valves and a ow-measuring device to provide a purging air supply, where the air source was a blended air cylinder. The temperature inside the dome was measured using a semiconductor temperature sensor mounted on the base-plate. The sensors were heated to 350 8C, measured by monitoring the resistance of the heater and calculating the temperature by use of the temperature coefcient of resistance. Each sensor lm was connected through a Keithley 7001 scanner to a Keithley 617 electrometer (Keithley Instruments, Reading, Berkshire, UK). Both Keithley instruments were connected via an IEEE488 interface to an IBM-compatible computer. The conductances of the sensors were measured by applying a dc voltage of 0.1 V across the electrodes, and monitoring the current owing through the lm. Software written in-house permitted the automated gathering of sensor temperature, sensor conductance, chamber temperature and purge ow-rate data. Sensors prepared as described above were tested for their responses to ethanol vapour in the range 11000 ppb.

3. Results and discussion The screen-printed sensors were produced and tested initially. The choice for these sensors of a 50/50 mix by mass of tin dioxide and zinc oxide was based on earlier results that indicated that these proportions were optimum. The results for two of these sensors when exposed to ethanol vapour at concentrations of 10, 50, 100, 200, 300, 400, 500 and 1000 ppb are shown in Fig. 1. It can be seen that the sensors display an almost linear response over this range, and that the responses of different sensors are substantially similar. Subsequently, thick-lm paste sensors were produced based on a range of proportions of tin dioxide and zinc oxide.

Fig. 1. Responses (percentage change in conductance) of two screenprinted tin dioxide/zinc oxide mixed sensors to concentrations of ethanol vapour in the range 0.011.0 ppm.

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Fig. 2. Responses (percentage change in conductance) of five thick-film paste sensors (mass percentage ratios 100:0, 75:25, 50:50, 25:75 and 0:100 SnO2:ZnO, respectively) three types of Figaro sensors (TGS800, TGS822 and TGS842), and a screen-printed 50:50 SnO2:ZnO sensor to 10 and 100 ppb of ethanol vapour.

These sensors, as well as some commercially-available Figaro sensors, were tested at concentrations of 10 and 100 ppb of ethanol vapour. The results may be seen in Fig. 2, which incorporates also the responses of the screen-printed sensors at these concentrations. The results shown in Fig. 2 indicate how sensitive the tin dioxide/zinc oxide sensors were compared to the Figaro sensors. The results also show that the sensors based on zinc oxide alone were slightly more sensitive to ethanol than sensors based on tin dioxide alone, but that the most sensitive were the paste sensors consisting of 25% tin dioxide mixed with 75% zinc oxide. At 100 ppb of ethanol vapour, this type of sensor exhibited a response that was more than twice that of the screen-printed sensors, and almost 60 times greater than that of the most sensitive Figaro sensor (TGS822). Due to differences in the production techniques and the electrode geometry a direct comparison between the sensitivity of the thick-lm sensors and the screen-printed sensors proves difcult. However, in this and previous work [10] we have found thick-lm sensors to exhibit higher sensitivity than their thin lm counterparts. The mechanical stability and cohesion of the screenprinted sensors was high compared to the thick-lm sensors. This is undoubtedly due to the differences in lm thickness and the effects of the binder. However, the mechanical stability and baseline stability of the thick-lm sensors was appreciable and they have been operated successfully in sensor systems for up to 12 months. Whilst sintering at high temperatures does increase the stability and cohesion of the layer it often results in a loss of sensitivity and associated binders can alter the sensing properties. The production method for the thick-lm sensors is facile when compared

to that of the screen-printed sensors, and although there is a loss of stability this is offset by an enhancement in sensitivity. The enhanced sensitivity of the tin dioxide/zinc oxide sensors has also been found in their responses to other vapours [10]. In these cases it was found that tin dioxide and zinc oxide were both catalytically active, but that each promoted different breakdown proles of the vapours being sensed. Because of their complementary catalytic activity, the mixed oxides permitted a more complete breakdown of the vapours, leading to the observed enhancement in sensitivity. Ethanol is frequently a major breakdown product of foodstuffs colonised by bacteria or fungi. Where foodstuffs such as grain or potato tubers are stored in bulk, disease can spread rapidly once an infection has become established resulting in signicant losses. Therefore, sensitive ethanol sensors are necessary to detect as early as possible the onset of spoilage so that remedial measures can be taken. Tin dioxide/zinc oxide sensors of the type described here have found practical use as elements of a sensor array in an electronic nose for the detection of diseases such as soft rot (Erwinia carotovora) in stored potato tubers [11].

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