Anda di halaman 1dari 8

Sensors and Actuators B (1998) 52 59

NOx gas sensing characteristics of WO3 thin lms activated by noble metals (Pd, Pt, Au) layers
M. Penza *, C. Martucci, G. Cassano
PASTIS -CNRSM, SS. 7, Appia, Km 7 + 300 per Mesagne, I -72100 Brindisi, Italy Received 27 November 1997; received in revised form 27 April 1998; accepted 30 April 1998

Abstract WO3-based gas sensor devices have been fabricated by reactive rf sputtering on glass substrates. Palladium (Pd), platinum (Pt), ) were evaporated as activator layers onto WO3 thin lms and Al layers (1500 A ) were gold (Au) noble metals (100600 A sputtered on top of them as upper electrodes for sensor output. The described sensing element was found to possess excellent sensitivity towards NO and NO2 gases, at low temperatures (100 300C). The optimum operating temperature was 150 and 200C for Pt, Pd and Au, respectively. The resistance of the thin-lm gas sensor increases reversibly in the presence of low concentrations of NO (0440 ppm) and NO2 (010 ppm) gases in air. The activator layers have an promotional effect on the speed of response to NOx at low temperatures and on selectivity enhanced with respect to other reducing gases (CO, CH4, H2, SO2, H2S, NH3). The temperature dependence of response and recovery times has been examined. The inuence of the thickness of the noble metals on NOx gases sensitivity has been investigated. The NO and NO2 gases calibration curves have been recorded for the optimum performances of each fabricated sensor-device. 1998 Elsevier Science S.A. All rights reserved.
Keywords: NOx gas sensor; WO3 thin lms; Pd, Pt, Au activator layers

1. Introduction It is well known that the detection and the emission control of nitrogen oxides (NO, NO2) are crucial points to reduce the noxious effects on environment and human beings. For instance, acid rains, photochemical smog, production of ozone, seem to be some of the effects caused by the increased amount of nitrogen oxides air-released through combustion chemical plants, automobiles. In case of exhaust gases from power stations, the main component of air-emitted NOx mixture is NO (90 95% in total) ranging 0 to 4000 ppm. In case of environmental monitoring, the threshold limit value (TLV) for NO2 and NO is 3 and 25 ppm, respectively, as listed in the safety standards by the American Conference of Governmental Industrial Hy-

* Corresponding author. Tel.: + 39 831 507374; fax: + 39 831 507379; e-mail: penza@cnrsm.it 0925-4005/98/$19.00 1998 Elsevier Science S.A. All rights reserved. PII S0925-4005(98)00156-7

gienist (ACGIH). Therefore, a NOx sensor requires high sensitivity at low concentrations comparable to the corresponding TLVs. Semiconductor gas sensors based on metal oxides have been studied extensively [13]. WO3 seems to be the most promising material as NOx gas sensor [48]. In a previous publication [9] we reported on good sensitivity of the sputtered WO3 thin lms towards NOx gas. It was found that the optimal operating temperature to detect NOx was about 250C. Moreover, the sensing characteristics of the WO3 thin lms have been investigated by surface acoustic waves (SAW) devices [10]. In the latter work we discussed some possible sensing mechanisms and the specicity of the WO3 thin lms to sense NOx. In the present paper, we show that the sensitivity, the minimum level of NOx gas detection, the selectivity can be signicantly improved by addition of thin layers of noble metals such as palladium (Pd), platinum (Pt), gold (Au) on the surface of the WO3 thin lms operating at low sensor temperatures.

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

53

2. Experimental

2.1. Fabrication of the sensing element


The tungsten trioxide lms were prepared by a reactive rf sputtering system, the details of which are described elsewhere [11]. A target of 4N purity W with diameter of 10 cm and thickness of 3 mm was used. The target-substrate distance was xed at 5 cm. The substrates of glass (7059 Corning), sized 15 15 mm and thickness of 5 mm, were held in thermal contact to a planetary-rotary holder during deposition. The substrate temperature was kept constant during lm deposition at 300C. The sputtering gas atmosphere in the chamber consisted of Ar O2 mixture with ratio 2/8 of their controlled ow rates, respectively. The pressure in chamber during deposition was measured as 6 10 2 mbar. Before deposition, the chamber was evacuated down to the low 10 7 mbar range by a turbomolecular pump. The tungsten trioxide lms were grown at an s 1. The thickness of average deposition rate of 0.3 A WO3 lms was xed at 3000 A. The sheet resistance of lms was as high as 109 V/square, at room temperature. After each deposition, the lms were annealed at 400C in dry air at least 6 h to complete the oxidation process and stabilise the sensing properties. Two Al metallised strips were sputtered on the top of the WO3 lm surface in order to serve as electrical contacts of the sensing element. Each Al strip was thick. The cross section of the 2 15 mm and 1500 A thin-lm sensor is depicted in Fig. 1. Thin lms of the noble metals (Pd, Pt, Au) were separately deposited onto the surface of the WO3, between the Al strips, by vacuum thermal evaporation using a tungsten boat. The area of deposition was 7 15 mm. Vacuum evaporation was carried out under a working pressure of 2 10 5 mbar after initial evacuation of chamber to 1 10 6 mbar. The evaporation s 1 for Pd, 0.2 A s 1 for Pt, 6 A s1 rate was 0.5 A for Au and the thickness of the lms, ranging from 100 , was controlled by a thickness monitor in situ to 600 A based on quartz oscillation method. After evaporation,

Fig. 2. Sensor sensitivity to NO2 gas and NO gas versus operating ) sensor and for WO3 samples temperature for undoped WO3 (3000 A activated by Pd, Pt, Au catalytic layers. The thickness of all catalysts . was 600 A

the thickness of the lms was measured by an alphastep prolometer in order to estimate the effective deposition rate of the lms.

2.2. Measurements of the sensing characteristics


Before gas testing, the thin-lm devices were annealed at 200C for at least 1 h in air to stabilise the sensing properties of the activator layers. The gas sensing experiments were carried out by introducing the thin-lm device thus prepared into a thermostatted test cell (250 ml volume), which was

Fig. 1. Scheme of the sensing element.

54

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

placed in series with a mass ow controller driving eight separate ow meters connected to two distinct gas-mixers, one for reference ambient and the other for test ambient. The accuracy of each gas ow meter was 9 1% of its full scale. All gases were injected parallel to the lm surface at same total ow rate of 500 ml min 1. Dry air was used both as reference gas and as diluting gas to obtain gas mixtures with different concentrations. The gases under test were: 0 10 ppm NO2; 0 440 ppm NO; 1000 ppm CO; 7000 ppm CH4; 10 ppm H2S; 10 ppm SO2; 500 ppm NH3; 500 ppm H2 in

air. The sensing element operated in the temperature range 100300C. The sensor temperature was measured by a thermocouple of chromelalumel, the d.c. output voltage of which was read-out by a multimeter (HP 34401 A). The electrical characteristics of the WO3 lms were obtained measuring the electrical current owing through lms biased by constant voltage. A multimeter (HP 34401 A) or a programmable electrometer (Keithley 617) was used to measure the d.c. electrical resistance of the sensor. All measurement parameters were controlled and acquired with a personal computer by means of IEEE interfaces and a VEE home-made software. The initial electrical characteristics of the thinlm sensor were stabilised in dry air at the operating temperature for at least 1 h, before any test gas exposure. The sensor response was dened as Rg/Ro or Ro/Rg for the oxidising gases and the reducing gases, respectively, where Rg and Ro were the electrical resistance of the sensor in presence of the gas under test and in air, respectively. By assuming a linear regression for the calibration curves of the sensor at each operating temperature, the sensor sensitivity S was dened as the slope of the output signal, (Rg/Ro) or (Ro/Rg) according to the type of gas under test, as a function of the gas concentration (ppm) in the examined range.

3. Results and discussion The sensor sensitivity S, calculated as cited in the previous paragraph, towards NO2 and NO gases as a function of sensor temperature is shown in Fig. 2 for ) thin lm sensor activated separately the WO3 (3000 A by Pd, Pt, Au catalysts having the same thickness of . The sensitivity for the undoped WO3 thin lm 600 A ) towards NO2 and NO is also reported. The (3000 A temperature for the maximum sensitivity to NOx corresponds to about 150 and 200C for Pt/WO3, Au/WO3 and Pd/WO3, respectively and 250C for the undoped WO3. It can be seen that the effect of the noble metals is twofold: (a) to lower the best operating sensor temperature; and (b) to enhance the sensitivity to NOx gases with respect to undoped WO3, as expected for an efcient catalyst. The maximum sensitivity to NOx gases is obtained by Pd lm at the best operating temperature of 200C, although the Pt lm is able to maximise the sensitivity at a lower operating temperature (150C), as noted in Fig. 2. Moreover, the NO2 sensitivity is higher than NO sensitivity for both any examined catalysed-WO3 sensor and undoped WO3 sensor [9], in the whole investigated temperature range. The enhanced sensing characteristics observed may be attributed to the typical effects of agglomeration of the catalysts on the surface of the WO3 lm.

Fig. 3. Sensor response to 10 ppm NO2 and 440 ppm NO as a function of thickness of different catalytic layers (Pd, Pt, Au). The sensor temperature was the maximum operating temperature: 200C for Pd and Au; 150C for Pt. The thickness of WO3 thin lm was for each device. 3000 A

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

55

Fig. 4. Transient responses of the WO3-based gas sensor towards pulses of (a) NO2 gas (10 to 1 ppm) and (b) NO gas (440 to 20 ppm), at maximum operating temperature (200C for Pd/WO3 and Au/WO3; 150C for Pt/WO3) for each device. The gas detector was activated by 600 thick Pd, Pt, Au lms, respectively. The thickness of WO3 thin lm was xed at 3000 A for each device. The exposure time was kept constant A at 5 min for each test gas sampling.

56

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

thick Pd, Pt, Au lms, respectively, Fig. 5. Calibration curves of the undoped WO3-based gas sensor and of the gas detectors activated by 600 A towards (a) NO2 gas and (b) NO gas, at maximum operating temperature (250C for undoped sample, 200C for Pd/WO3 and Au/WO3; 150 C for each device. for Pt/WO3) for each device. The thickness of WO3 thin lm was xed at 3000 A

The sensor response towards 10 ppm NO2 and 440 ppm NO gases as a function of the thickness of Pd, Pt, Au catalysts was investigated. The measuring temperature was the maximum operating temperature of each catalysed-WO3 sensor. The results are indicated in Fig. 3. For each device investigated, the sensor response to NO2 and NO increases with the thickness of the activator layer in the examined thickness range and the best thick catalyst: performances are obtained with 600 A thick for instance, by adding 600 A Pd onto 3000 A WO3 lm, Rg/Ro is equal to 6.5 and 100.3 for 10 ppm NO2 and 440 ppm NO, respectively. The transient responses of the WO3-sensing elements ) of activated separately by the same thickness (600 A Pd, Pt, Au towards on-off turning cycles of 10 to 1 ppm NO2 and 440 to 20 ppm NO in air are shown in Fig. 4a and b, respectively. The operating temperature of the devices is 150 and 200C for Pt/WO3, Pd/WO3 and Au/WO3, respectively. Generally, the resistance increased upon NO and NO2 exposures, as expected for a n -type semiconductor like WO3 working in presence of oxidising gases such as NOx. The peculiar feature of the response of the WO3:Pd sensor towards NO2 gas could be caused by two competitive effects: (a) direct adsorption of charge carriers from lm conduction band generates the initial increase of the sensor resistance upon exposure of NO2 gas with high oxidising power. This process can be differently promoted by the catalysts; and (b) desorption of oxygen species (O , O2 , O2 2 ), precedently ionosorbed onto lm surface, with consequent release of charge carriers to the lm conduction

band generates the decrease of the resistance of the sensor upon NO2 gas exposure. However, the causes of the peculiar shape of the sensor response have not been completely claried yet. For the successive considerations, the value used as response of the WO3:Pd sensor towards NO2 gas is the nal value of lm resistance at the end of the exposure time. Moreover, a different kinetics has been observed for all catalysed sensors upon NO gas exposure in comparison to that of sensors upon NO2 gas exposure. Among the various reasons of the different behaviour, we should indicate the characteristic feature of NO gas oxidised into NO2 to be sensed by doped WO3-lms [10], the geometry of the parallel electrodes type [3], the important role of the lm surface states and agglomeration of the catalysts. The calibration curves of the undoped WO3-based gas sensor and of the gas detectors activated by 600 A thick Pd, Pt, Au lms towards NO2 and NO gases, at maximum operating temperature (250C for undoped sample, 200C for Pd and Au, 150C for Pt) for each device, are shown in Fig. 5a and b, respectively. For any device investigated, the magnitude of sensor response increases linearly with the NOx gas concentration and the NOx sensitivity of the doped-sensors is higher than that of the undoped sensor. Consequently, a lower minimum level of gas can be detected, e.g. 1 ppm NO2 and 20 ppm NO are easily sensed by Pddoped WO3 lm. Since the NOx sensitivity of the doped-sensors has been enhanced, a sub-ppm level (especially NO2) seems possible to be detected at low

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

57

operating temperatures. However, the detected levels of 1 ppm NO2 and 20 ppm NO are useful for practical applications, because they are lower than the corresponding TLVs (3 ppm for NO2 and 25 ppm NO). Fig. 6 shows the response times, dened as the time needed to reach 90% of the nal steady value of the sensor-resistance after steply test gas injection, as a function of the operating temperature for undoped WO3-based gas sensor and the gas detectors activated by thick Pd, Pt, Au lms towards 10 ppm NO2 and 600 A

Fig. 7. Recovery time towards 10 ppm NO2 and 440 ppm NO versus operating temperature for the undoped WO3-based gas sensor and for thick Pd, Pt, Au lms, respecthe gas detectors activated by 600 A for each tively. The thickness of WO3 thin lm was xed at 3000 A device.

Fig. 6. Response time towards 10 ppm NO2 and 440 ppm NO versus operating temperature for the undoped WO3-based gas sensor and for thick Pd, Pt, Au lms, respecthe gas detectors activated by 600 A for each tively. The thickness of WO3 thin lm was xed at 3000 A device.

440 ppm NO gases. In the case of the WO3:Pd sensor, the response time has been taken as the time at the valley of sensor response upon NO2 gas exposure (see Fig. 4a, e.g. 10 ppm NO2). For the examined gas detectors, the response times decrease with the temperature and the Pd-, Pt-, Au-doped samples exhibit speed of response higher than the undoped sample. As an example 2.7 and 2.8 min towards 10 ppm NO2 and 440 ppm NO, respectively, at 200C for the Pd-doped WO3 lm against 4 and 4.1 min towards 10 ppm NO2 and 440 ppm NO, respectively, at 200C for the undoped WO3 lm.

58

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

Table 1 Sensor response, (Rg/Ro) or (Ro/Rg), towards oxidising or reducing gases with different gas concentrations, of the undoped WO3-based sensor and thick Pd, Pt, Au lms, respectively, at best operating temperature (250C for undoped sample, 200C for of the detectors activated by 600 A for each device Pd/WO3 and Au/WO3; 150C for Pt/WO3) for each device. The thickness of WO3 thin lm was 3000 A Test gas 10 ppm NO2 440 ppm NO 1000 ppm CO 7000 ppm CH4 10 ppm H2S 10 ppm SO2 500 ppm NH3 500 ppm H2 WO3 (250C) (Rg/Ro) = 2.0 (Rg/Ro) = 40 (Ro/Rg) = 0.05 (Ro/Rg) = 1.05 (Ro/Rg) = 0.85 (Ro/Rg) = 0.4 (Ro/Rg) = 0.32 (Ro/Rg) = 0.01 WO3:Pd (200C) (Rg/Ro) = 6.51 (Rg/Ro) = 100.3 (Ro/Rg) = 0.05 (Ro/Rg) = 1.12 (Ro/Rg) = 1.3 (Ro/Rg) = 0.2 (Ro/Rg) = 0.56 (Ro/Rg) = 0.09 WO3:Pt (150C) (Rg/Ro) = 3.45 (Rg/Ro) = 70.4 (Ro/Rg) = 0.05 (Ro/Rg) = 1.19 (Ro/Rg) = 1.1 (Ro/Rg) = 0.3 (Ro/Rg) = 0.65 (Ro/Rg) = 0.02 WO3:Au (200C) (Rg/Ro) = 4.8 (Rg/Ro) = 78 (Ro/Rg) = 0.06 (Ro/Rg) = 1.26 (Ro/Rg) = 1.5 (Ro/Rg) = 0.4 (Ro/Rg) = 0.5 (Ro/Rg) = 0.04

Fig. 7 shows the recovery times, dened as the time needed to return to 90% of the initial steady value of the sensor-resistance after steply recovery gas injection, as a function of the operating temperature for undoped WO3-based gas sensor and the gas detectors thick Pd, Pt, Au lms towards 10 activated by 600 A ppm NO2 and 440 ppm NO gases. For the examined gas detectors, the recovery times decrease with the temperature and the Pd-, Pt-, Au-doped samples exhibit speed of recovery higher than the undoped sample. As an example: 4 and 4.5 min towards 10 ppm NO2 and 440 ppm NO, respectively, at 200C for the Pd-doped WO3 lm against 12 and 19 min towards 10 ppm NO2 and 440 ppm NO, respectively, at 200C for the undoped WO3 lm. Taking into account the results of sensitivity (Fig. 2), transient responses (Fig. 4a and b), response time (Fig. 6), recovery time (Fig. 7), we can conclude that the better compromise between sensitivity and response and recovery times has been obtained for Pddoped WO3 sensor at 200C to detect NOx gas. Unfortunately, the Pd-, Pt-, Au-doped WO3 lms did not have enough long-term stability. After approximately 2 weeks, NOx gas sensitivities were strongly decreased and the baseline resistances were strongly increased due to well-known ageing effects of the catalysts. A better stabilisation of the Pd-, Pt-, Au-doped WO3-based sensors could be obtained by using inert lters covering the surface of the sensor without appreciable lowering of the sensitivities of the fresh doped WO3 samples. This methodics was efciently used for the Pd- and Pt-doped SnO2 sensors [12]. In order to investigate the catalysts inuence on sensitivity of WO3-detectors Pd-, Pt-, Au-activated towards some interfering gases of NOx, experiments of gases testing have been carried by using the devices operating under their best working conditions (sensor temperature and catalyst thickness). The results obtained are shown in Table 1. It can be seen that the responses to NO2 and NO oxidising gases have been

increased by Pd, Pt, Au activator layers with respect to those of the undoped WO3 sample. The highest NOx response has been obtained by Pd lm. Moreover, the responses towards other reducing gases (CO, CH4, H2S, SO2, NH3, H2) of the activated sensors are approximately unchanged with respect to those of the undoped WO3 sample, excluding the H2S response enhanced by each activator layer and maximised by Au lm, as expected for the typical effects of Au-doped WO3 on H2S gas [13]. Therefore, the effect of the catalysts on WO3 sensor is the better selectivity achieved towards NOx gases with respect to the reducing gases tested, at low temperatures.

4. Conclusions WO3-based thin lm sensor devices have been fabricated by reactive rf sputtering with evaporated activator layers of Pd, Pt, Au. These sensors are very promising for NO2 and NO gas detection at low temperatures (150250C). Best performances have been obtained at 150, 200, 250C for WO3:Pt, WO3:Pd and WO3:Au, undoped WO3, respectively, thick catalyst. Under these working with 600 A conditions, a level of 1 ppm NO2 and 20 ppm NO has been detected by Pd-activated WO3-sensor and a sub-ppm NO2 concentration results accessible. The better compromise between sensitivity and response and recovery times has been obtained for Pd-doped WO3 sensor at 200C to detect NOx gas. The activation of the WO3-sensor devices by deposition of Pd, Pt, Au lms has been observed to enhance the selectivity towards NOx with respect to the reducing gases (CO, CH4, H2, SO2, H2S, NH3), excluding H2S and to exhibit better responses and recovery times with respect to undoped WO3-sensor. Some drawbacks are not yet solved such as the ageing of catalysts, the stability of doped WO3-lms, the complete understanding of the peculiarities in the shape of the doped WO3 based-sensor response.

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259

59

Acknowledgements This work was nancially supported by Enea in the framework Intesa Enea-Murst under project 4335/04. The authors are indebted to F. Musio and G. Montagna for the implementation of the data acquisition system and the equipments interfaces.

tors B 15 16 (1993) 384 389. [13] D.J. Smith, J.F. Vetelino, R.S. Falconer, E.L. Wittman, Stability, sensitivity and selectivity of tungsten trioxide lms for sensing applications, Sensors and Actuators B 13 14 (1993) 264 268.

Biographies References
[1] V. Demarne, R. Sanjines, Thin lm semiconducting metal oxide gas sensors, in: G. Sberveglieri (Ed.), Gas Sensors, Kluwer, Dordrecht, 1992, pp. 89 116. [2] G. Faglia, G. Benussi, L. Depero, G. Dinelli, G. Sberveglieri, NO2 sensing by means of SnO2 (Al) thin lms grown by rheotaxial growth and thermal oxidation technique, Sensors and Materials 8 (4) (1996) 239 249. [3] T. Inoue, K. Ohtsuka, Y. Yoshida, Y. Matsuura, Y. Kajiyama, Metal oxide semiconductor NO2 sensor, Sensors and Actuators B 2425 (1995) 388 391. [4] N. Yamazoe, N. Miura, New approaches in the design of gas sensors, in: G. Sberveglieri (Ed.), Gas Sensors, Kluwer, Dordrecht, 1992, pp. 1 42. [5] G. Sberveglieri, L. Depero, S. Groppelli, P. Nelli, WO3 sputtered thin lms for NOx monitoring, Sensors and Actuators B 26 27 (1995) 89 92. [6] C. Cantalini, M. Pelino, H.T. Sun, M. Faccio, S. Santucci, L. Lozzi, M. Passacantando, Cross sensitivity and stability of NO2 sensors from WO3 thin lm, Sensors and Actuators B 35 36 (1996) 112 118. [7] M. Akiyama, J. Tamaki, N. Miura, N. Yamazoe, Tungsten oxide-based semiconductor sensor highly sensitive to NO and NO2, Chem. Lett. (1991) 16111614. [8] K. Toda, K. Ochi, I. Sanemasa, NO-sensing properties of Au thin lm, Sensors and Actuators B 32 (1996) 1518. [9] M. Penza, M.A. Tagliente, L. Mirenghi, C. Gerardi, C. Martucci, G. Cassano, Tungsten trioxide (WO3) sputtered thin-lms for a NOx gas sensor, Sensors and Actuators B 50 (1998) 918. [10] M. Penza, L. Vasanelli, SAW NOx gas sensor using WO3 thin-lm sensitive coatings, Sensors and Actuators B 41 (1997) 3136. [11] M. Penza, C. Martucci, V.I. Anisimkin, L. Vasanelli, Deposition of doped and undoped ZnO thin lms for gas sensors, Mater. Sci. Forum 203 (1996) 137142. [12] P. Dutronc, C. Lucat, F. Menil, M. Loesch, M.C. Horrillo, I. Sagayo, J. Gutierrez, J.A. de Agapito, A potentially selective methane sensor based on the differential conductivity response of Pd- and Pt-doped tin oxide thick layers, Sensors and Actua-

Michele Penza, born in 1964, graduated in Physics from the University of Bari (Italy) in 1990. He was a fellow of the Istituto Nazionale Fisica Materia (INFM) in 1991. Since 1992 he has worked at PASTISCNRSM, Brindisi (Italy) rst as fellow and then as researcher of the staff. His main activity is the physical preparation and characterisation of metallic and metal oxide thin solid lms for electrical and acoustic devices, especially SAW sensors for gases and vapours detection. He has co-authored 15 scientic papers and has attended international workshops and schools. He was abroad for scientic training at the Russian Academy of Sciences in 1993. He is IEEE Member, UFFC Member, Member of New York Academy of Sciences, Member of Italian Physical Society and Member of Italian Association on Sensors and Microsystems (AISEM). Concetta Martucci, born in 1963, obtained chemist diploma in 1982. Since 1990, she was fellow at CNRSM and then, starting from 1992 she has worked as technician in the staff of PASTIS-CNRSM. Her main activity is devoted to preparation of metal-oxide lms by PVD techniques. She spent a 1-year-period for scientic training at CNR-IESS, Rome and attended to various technical workshops. Gennaro Cassano, born in 1963, obtained electrotechnical diploma in 1984. Since 1990, he was fellow at CNRSM and then, starting from 1992 he has worked as technician in the staff of PASTIS-CNRSM. His main activity is devoted to electrical characterisation of thinlm gas sensors. He spent a 1-year-period for scientic training at CNR-MASPEC, Parma (Italy) and attended to various technical workshops.