Sensors and Actuators B (1998) 5259

NO
x
gas sensing characteristics of WO
3
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
WO
3
-based gas sensor devices have been fabricated by reactive rf sputtering on glass substrates. Palladium (Pd), platinum (Pt),
gold (Au) noble metals (100600 A

) were evaporated as activator layers onto WO

3
thin lms and Al layers (1500 A

) were
sputtered on top of them as upper electrodes for sensor output. The described sensing element was found to possess excellent
sensitivity towards NO and NO
2
gases, at low temperatures (100300C). 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 NO
2
(010 ppm) gases in air. The activator layers have an promotional effect on the speed of response
to NO
x
at low temperatures and on selectivity enhanced with respect to other reducing gases (CO, CH
4
, H
2
, SO
2
, H
2
S, NH
3
). The
temperature dependence of response and recovery times has been examined. The inuence of the thickness of the noble metals on
NO
x
gases sensitivity has been investigated. The NO and NO
2
gases calibration curves have been recorded for the optimum
performances of each fabricated sensor-device. 1998 Elsevier Science S.A. All rights reserved.
Keywords: NO
x
gas sensor; WO
3
thin lms; Pd, Pt, Au activator layers
1. Introduction
It is well known that the detection and the emission
control of nitrogen oxides (NO, NO
2
) are crucial points
to reduce the noxious effects on environment and hu-
man 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 NO
x
mixture is NO
(9095% in total) ranging 0 to 4000 ppm.
In case of environmental monitoring, the threshold
limit value (TLV) for NO
2
and NO is 3 and 25 ppm,
respectively, as listed in the safety standards by the
American Conference of Governmental Industrial Hy-
gienist (ACGIH). Therefore, a NO
x
sensor requires
high sensitivity at low concentrations comparable to the
corresponding TLVs.
Semiconductor gas sensors based on metal oxides
have been studied extensively [13]. WO
3
seems to be
the most promising material as NO
x
gas sensor [48].
In a previous publication [9] we reported on good
sensitivity of the sputtered WO
3
thin lms towards NO
x
gas. It was found that the optimal operating tempera-
ture to detect NO
x
was about 250C. Moreover, the
sensing characteristics of the WO
3
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 WO
3
thin
lms to sense NO
x
.
In the present paper, we show that the sensitivity, the
minimum level of NO
x
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 WO
3
thin lms operat-
ing at low sensor temperatures.
* 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
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 reac-
tive rf sputtering system, the details of which are de-
scribed 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 sub-
strates of glass (7059 Corning), sized 1515 mm and
thickness of 5 mm, were held in thermal contact to a
planetary-rotary holder during deposition. The sub-
strate temperature was kept constant during lm depo-
sition at 300C. The sputtering gas atmosphere in the
chamber consisted of ArO
2
mixture with ratio 2/8 of
their controlled ow rates, respectively. The pressure in
chamber during deposition was measured as 610
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
average deposition rate of 0.3 A

s
1
. The thickness of
WO
3
lms was xed at 3000 A

. The sheet resistance of

lms was as high as 10
9
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 WO
3
lm surface in order to serve as electrical
contacts of the sensing element. Each Al strip was
215 mm and 1500 A

thick. The cross section of the

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 WO
3
,
between the Al strips, by vacuum thermal evaporation
using a tungsten boat. The area of deposition was
715 mm. Vacuum evaporation was carried out under
a working pressure of 210
5
mbar after initial evac-
uation of chamber to 110
6
mbar. The evaporation
rate was 0.5 A

s
1
for Pd, 0.2 A

s
1
for Pt, 6 A

s
1
for Au and the thickness of the lms, ranging from 100
to 600 A

, was controlled by a thickness monitor in situ

based on quartz oscillation method. After evaporation,
Fig. 2. Sensor sensitivity to NO
2
gas and NO gas versus operating
temperature for undoped WO
3
(3000 A

) sensor and for WO

3
samples
activated by Pd, Pt, Au catalytic layers. The thickness of all catalysts
was 600 A

.
the thickness of the lms was measured by an alpha-
step 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 an-
nealed 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.
M. Penza et al. / Sensors and Actuators B 50 (1998) 5259 54
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
91% 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 con-
centrations. The gases under test were: 010 ppm NO
2
;
0440 ppm NO; 1000 ppm CO; 7000 ppm CH
4
; 10
ppm H
2
S; 10 ppm SO
2
; 500 ppm NH
3
; 500 ppm H
2
in
air. The sensing element operated in the temperature
range 100300C. The sensor temperature was mea-
sured by a thermocouple of chromel alumel, the d.c.
output voltage of which was read-out by a multimeter
(HP 34401 A).
The electrical characteristics of the WO
3
lms were
obtained measuring the electrical current owing
through lms biased by constant voltage. A multimeter
(HP 34401 A) or a programmable electrometer (Keith-
ley 617) was used to measure the d.c. electrical resis-
tance of the sensor. All measurement parameters were
controlled and acquired with a personal computer by
means of IEEE interfaces and a VEE home-made soft-
ware. The initial electrical characteristics of the thin-
lm sensor were stabilised in dry air at the operating
temperature for at least 1 h, before any test gas expo-
sure. The sensor response was dened as R
g
/R
o
or
R
o
/R
g
for the oxidising gases and the reducing gases,
respectively, where R
g
and R
o
were the electrical resis-
tance 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, (R
g
/R
o
) or (R
o
/R
g
) 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 NO
2
and NO gases as a
function of sensor temperature is shown in Fig. 2 for
the WO
3
(3000 A

) thin lm sensor activated separately

by Pd, Pt, Au catalysts having the same thickness of
600 A

. The sensitivity for the undoped WO

3
thin lm
(3000 A

) towards NO
2
and NO is also reported. The
temperature for the maximum sensitivity to NO
x
corre-
sponds to about 150 and 200C for Pt/WO
3
, Au/WO
3
and Pd/WO
3
, respectively and 250C for the undoped
WO
3
. It can be seen that the effect of the noble metals
is twofold: (a) to lower the best operating sensor tem-
perature; and (b) to enhance the sensitivity to NO
x
gases with respect to undoped WO
3
, as expected for an
efcient catalyst. The maximum sensitivity to NO
x
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 tempera-
ture (150C), as noted in Fig. 2. Moreover, the NO
2
sensitivity is higher than NO sensitivity for both any
examined catalysed-WO
3
sensor and undoped WO
3
sen-
sor [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 WO
3
lm.
Fig. 3. Sensor response to 10 ppm NO
2
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 WO
3
thin lm was
3000 A

for each device.

M. Penza et al. / Sensors and Actuators B 50 (1998) 5259 55
Fig. 4. Transient responses of the WO
3
-based gas sensor towards pulses of (a) NO
2
gas (10 to 1 ppm) and (b) NO gas (440 to 20 ppm), at
maximum operating temperature (200C for Pd/WO
3
and Au/WO
3
; 150C for Pt/WO
3
) for each device. The gas detector was activated by 600
A

thick Pd, Pt, Au lms, respectively. The thickness of WO

3
thin lm was xed at 3000 A

for each device. The exposure time was kept constant

at 5 min for each test gas sampling.
M. Penza et al. / Sensors and Actuators B 50 (1998) 5259 56
Fig. 5. Calibration curves of the undoped WO
3
-based gas sensor and of the gas detectors activated by 600 A

thick Pd, Pt, Au lms, respectively,

towards (a) NO
2
gas and (b) NO gas, at maximum operating temperature (250C for undoped sample, 200C for Pd/WO
3
and Au/WO
3
; 150 C
for Pt/WO
3
) for each device. The thickness of WO
3
thin lm was xed at 3000 A

for each device.

The sensor response towards 10 ppm NO
2
and 440
ppm NO gases as a function of the thickness of Pd, Pt,
Au catalysts was investigated. The measuring tempera-
ture was the maximum operating temperature of each
catalysed-WO
3
sensor. The results are indicated in Fig.
3. For each device investigated, the sensor response to
NO
2
and NO increases with the thickness of the activa-
tor layer in the examined thickness range and the best
performances are obtained with 600 A

thick catalyst:
for instance, by adding 600 A

Pd onto 3000 A

thick
WO
3
lm, R
g
/R
o
is equal to 6.5 and 100.3 for 10 ppm
NO
2
and 440 ppm NO, respectively.
The transient responses of the WO
3
-sensing elements
activated separately by the same thickness (600 A

) of
Pd, Pt, Au towards on-off turning cycles of 10 to 1 ppm
NO
2
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/WO
3
, Pd/WO
3
and
Au/WO
3
, respectively. Generally, the resistance in-
creased upon NO and NO
2
exposures, as expected for a
n-type semiconductor like WO
3
working in presence of
oxidising gases such as NO
x
. The peculiar feature of the
response of the WO
3
:Pd sensor towards NO
2
gas could
be caused by two competitive effects: (a) direct adsorp-
tion of charge carriers from lm conduction band gen-
erates the initial increase of the sensor resistance upon
exposure of NO
2
gas with high oxidising power. This
process can be differently promoted by the catalysts;
and (b) desorption of oxygen species (O

, O
2

, O
2
2
),
precedently ionosorbed onto lm surface, with conse-
quent release of charge carriers to the lm conduction
band generates the decrease of the resistance of the
sensor upon NO
2
gas exposure. However, the causes of
the peculiar shape of the sensor response have not been
completely claried yet. For the successive consider-
ations, the value used as response of the WO
3
:Pd sensor
towards NO
2
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 compari-
son to that of sensors upon NO
2
gas exposure. Among
the various reasons of the different behaviour, we
should indicate the characteristic feature of NO gas
oxidised into NO
2
to be sensed by doped WO
3
-lms
[10], the geometry of the parallel electrodes type [3], the
important role of the lm surface states and agglomera-
tion of the catalysts.
The calibration curves of the undoped WO
3
-based
gas sensor and of the gas detectors activated by 600 A

thick Pd, Pt, Au lms towards NO

2
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 re-
sponse increases linearly with the NO
x
gas concentra-
tion and the NO
x
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 NO
2
and 20 ppm NO are easily sensed by Pd-
doped WO
3
lm. Since the NO
x
sensitivity of the
doped-sensors has been enhanced, a sub-ppm level (es-
pecially NO
2
) 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 NO
2
and 20 ppm NO are useful for practical
applications, because they are lower than the corre-
sponding TLVs (3 ppm for NO
2
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
WO
3
-based gas sensor and the gas detectors activated by
600 A

thick Pd, Pt, Au lms towards 10 ppm NO

2
and
Fig. 7. Recovery time towards 10 ppm NO
2
and 440 ppm NO versus
operating temperature for the undoped WO
3
-based gas sensor and for
the gas detectors activated by 600 A

thick Pd, Pt, Au lms, respec-

tively. The thickness of WO
3
thin lm was xed at 3000 A

for each
device.
Fig. 6. Response time towards 10 ppm NO
2
and 440 ppm NO versus
operating temperature for the undoped WO
3
-based gas sensor and for
the gas detectors activated by 600 A

thick Pd, Pt, Au lms, respec-

tively. The thickness of WO
3
thin lm was xed at 3000 A

for each
device.
440 ppm NO gases. In the case of the WO
3
:Pd sensor,
the response time has been taken as the time at the
valley of sensor response upon NO
2
gas exposure (see
Fig. 4a, e.g. 10 ppm NO
2
). For the examined gas
detectors, the response times decrease with the tempera-
ture and the Pd-, Pt-, Au-doped samples exhibit speed of
response higher than the undoped sample. As an exam-
ple 2.7 and 2.8 min towards 10 ppm NO
2
and 440 ppm
NO, respectively, at 200C for the Pd-doped WO
3
lm
against 4 and 4.1 min towards 10 ppm NO
2
and 440 ppm
NO, respectively, at 200C for the undoped WO
3
lm.
M. Penza et al. / Sensors and Actuators B 50 (1998) 5259 58
Table 1
Sensor response, (R
g
/R
o
) or (R
o
/R
g
), towards oxidising or reducing gases with different gas concentrations, of the undoped WO
3
-based sensor and
of the detectors activated by 600 A

thick Pd, Pt, Au lms, respectively, at best operating temperature (250C for undoped sample, 200C for
Pd/WO
3
and Au/WO
3
; 150C for Pt/WO
3
) for each device. The thickness of WO
3
thin lm was 3000 A

for each device

WO
3
:Pd (200C) Test gas WO
3
:Pt (150C) WO
3
(250C) WO
3
:Au (200C)
(R
g
/R
o
) =6.51 (R
g
/R
o
) =3.45 (R
g
/R
o
) =2.0 (R
g
/R
o
) =4.8 10 ppm NO
2
(R
g
/R
o
) =100.3 (R
g
/R
o
) =70.4 440 ppm NO (R
g
/R
o
) =78 (R
g
/R
o
) =40
(R
o
/R
g
) =0.05 (R
o
/R
g
) =0.05 (R
o
/R
g
) =0.05 (R
o
/R
g
) =0.06 1000 ppm CO
(R
o
/R
g
) =1.05 7000 ppm CH
4
(R
o
/R
g
) =1.12 (R
o
/R
g
) =1.19 (R
o
/R
g
) =1.26
(R
o
/R
g
) =1.3 (R
o
/R
g
) =1.1 (R
o
/R
g
) =0.85 (R
o
/R
g
) =1.5 10 ppm H
2
S
(R
o
/R
g
) =0.4 10 ppm SO
2
(R
o
/R
g
) =0.2 (R
o
/R
g
) =0.3 (R
o
/R
g
) =0.4
(R
o
/R
g
) =0.56 (R
o
/R
g
) =0.65 (R
o
/R
g
) =0.5 500 ppm NH
3
(R
o
/R
g
) =0.32
(R
o
/R
g
) =0.09 (R
o
/R
g
) =0.02 (R
o
/R
g
) =0.04 (R
o
/R
g
) =0.01 500 ppm H
2
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 injec-
tion, as a function of the operating temperature for
undoped WO
3
-based gas sensor and the gas detectors
activated by 600 A

thick Pd, Pt, Au lms towards 10

ppm NO
2
and 440 ppm NO gases. For the examined
gas detectors, the recovery times decrease with the
temperature and the Pd-, Pt-, Au-doped samples ex-
hibit speed of recovery higher than the undoped sam-
ple. As an example: 4 and 4.5 min towards 10 ppm
NO
2
and 440 ppm NO, respectively, at 200C for the
Pd-doped WO
3
lm against 12 and 19 min towards
10 ppm NO
2
and 440 ppm NO, respectively, at 200C
for the undoped WO
3
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 re-
sponse and recovery times has been obtained for Pd-
doped WO
3
sensor at 200C to detect NO
x
gas.
Unfortunately, the Pd-, Pt-, Au-doped WO
3
lms
did not have enough long-term stability. After ap-
proximately 2 weeks, NO
x
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 WO
3
-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 WO
3
samples. This methodics was ef-
ciently used for the Pd- and Pt-doped SnO
2
sensors
[12].
In order to investigate the catalysts inuence on
sensitivity of WO
3
-detectors Pd-, Pt-, Au-activated to-
wards some interfering gases of NO
x
, experiments of
gases testing have been carried by using the devices
operating under their best working conditions (sensor
temperature and catalyst thickness). The results ob-
tained are shown in Table 1. It can be seen that the
responses to NO
2
and NO oxidising gases have been
increased by Pd, Pt, Au activator layers with respect
to those of the undoped WO
3
sample. The highest
NO
x
response has been obtained by Pd lm. More-
over, the responses towards other reducing gases (CO,
CH
4
, H
2
S, SO
2
, NH
3
, H
2
) of the activated sensors are
approximately unchanged with respect to those of the
undoped WO
3
sample, excluding the H
2
S response en-
hanced by each activator layer and maximised by Au
lm, as expected for the typical effects of Au-doped
WO
3
on H
2
S gas [13]. Therefore, the effect of the
catalysts on WO
3
sensor is the better selectivity
achieved towards NO
x
gases with respect to the re-
ducing gases tested, at low temperatures.
4. Conclusions
WO
3
-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 NO
2
and NO gas detection at low
temperatures (150250C). Best performances have
been obtained at 150, 200, 250C for WO
3
:Pt,
WO
3
:Pd and WO
3
:Au, undoped WO
3
, respectively,
with 600 A

thick catalyst. Under these working

conditions, a level of 1 ppm NO
2
and 20 ppm NO
has been detected by Pd-activated WO
3
-sensor and a
sub-ppm NO
2
concentration results accessible. The
better compromise between sensitivity and response
and recovery times has been obtained for Pd-doped
WO
3
sensor at 200C to detect NO
x
gas. The
activation of the WO
3
-sensor devices by deposition of
Pd, Pt, Au lms has been observed to enhance the
selectivity towards NO
x
with respect to the reducing
gases (CO, CH
4
, H
2
, SO
2
, H
2
S, NH
3
), excluding H
2
S
and to exhibit better responses and recovery times
with respect to undoped WO
3
-sensor. Some
drawbacks are not yet solved such as the ageing of
catalysts, the stability of doped WO
3
-lms, the
complete understanding of the peculiarities in the
shape of the doped WO
3
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. Mon-
tagna for the implementation of the data acquisition
system and the equipments interfaces.
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Biographies
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 PASTIS-
CNRSM, 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 detec-
tion. 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 Mem-
ber, Member of New York Academy of Sciences, Mem-
ber 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 techni-
cian 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 electrotech-
nical 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 thin-
lm gas sensors. He spent a 1-year-period for scientic
training at CNR-MASPEC, Parma (Italy) and attended
to various technical workshops.
.