ELSEVIER Sensors and Actuators B 23 (1995) 103-109

cHBcAL
Recent developments in semiconducting thin-film gas sensors
G. Sberveglieri
Thin Film Laboratory, Department of Chemistry and Physics for Materials, University of Brescia, via Valotti, 9, 1-25133 Brescia, Italy
Received 15 September 1993; in revised form 27 September 1994; accepted 6 October 1994

Abstract

A critical review of thin-film semiconducting materials that are used as gas sensors is presented in this paper. These materials
can be approximately divided into two main groups: the first includes sensors that detect oxygen with variations of bulk or
surface conductance; the second comprises all the materials that detect oxidizing and reducing gases in air at constant oxygen
partial pressure by means of surface-conductance variations. The oxygen-detection mechanisms of surface- and bulk-conductance
sensors are described. The long-term stability and the selectivity to a particular species are the main properties of a reliable
gas sensor; these properties are also discussed in detail in relation to the second group of sensors. The properties of tin
oxide, the most investigated material for gas sensing, are reviewed; some new ternary semiconducting compounds are also
presented, together with their growth techniques. An almost novel method for growing thin films, the RGTO (rheotaxial
growth and thermal oxidation) technique will be presented, since it is capable of preparing mixed oxide thin films with high
surface area and nanosized crystallites. It is well known that the main possibility for sensor development lies in device arrays;
therefore, the utilization of different materials for gas detection and the measurement techniques of signals supplied by sensor
arrays will be outlined.

Keywords: Gas sensors; Semiconductors; Thin-film sensors

1. Introduction low-power-consumption sensors like the semiconducting

40 years ago, Bardeen et al. discovered [1] that gas
adsorption onto a semiconductor produces a conduc-
tance change; from that time, a great amount of research
was carried out in order to realize commercial semi-
conducting devices for gas detection.
SnO2 has been the most investigated material, the
first devices being based on a thick film or ceramic
layer of tin oxide [2]. Commercial devices are now
available; they use the conductance variations of sem-
iconducting metal oxides for detecting low concentra-
tions of flammable gases like CH4, L P G and H2 or
toxic gases like CO, H2S and NOx.
Moreover, oxygen sensors based on TiO2, Ga203 and
SrTiO3 are still in an advanced phase of development;
they operate at high temperature for detecting the gas
exhausted by car engines and during metallurgical pro-
cesses. These sensors show a good response to oxygen,
but unfortunately a poisoning effect is also present
after their utilization in the working environment [3].
Low concentrations of toxic gases like H2S, NH3,
AsH 3 and PH3 should also be detected by low-cost and
devices. The current research on gas sensors is aimed
at solving either the poor selectivity or the long-term
drift.
Two main lines are being developed in parallel. The
first consists in the modulation of properties that can
enhance the sensitivity to a particular gas and the long-
term stability; a promising way seems to be the control
of the grain size [4,5]. The second is the realization
of a sensor array composed of devices with quite good
sensitivity, selectivity and high stability, together with
electronic circuitry based on a microprocessor for the
elaboration of the sensor signals according to pattern-
recognition techniques [6]. In both these approaches,
thin-film technology seems to be the most suitable for
preparing gas sensors.
In fact, it allows the control of material composition
at a monolayer level and also the preparation of min-
iaturized devices with low cost and low power con-
sumption.
Different deposition methods like PVD, CVD and
sol-gel techniques can be used for the preparation of
thin-film gas sensors.

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104 G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109

2. Applications of semiconducting gas sensors where o- is the conductivity, C is a constant, EA is the

activation energy for the bulk conduction and Po~ is
Gas sensors are used for two main applications: (a) the oxygen partial pressure. The constant m, reported
oxygen detection at medium (473--873 K) and high in Table l(a) as the oxygen sensitivity, depends on the
(873-1373 K) temperatures; (b) detection of low gas defects involved in the conduction mechanism. When
concentrations at medium temperature (473-773 K) the defects are represented by doubly ionized oxygen
and constant oxygen pressure. vacancies, m = - 6 , while if the defects are represented
by metal vacancies, different values of m are found.
2.1. Oxygen detection with semiconducting thin films Some binary compounds like Ga203 and TiO2 were
tested for oxygen detection; recently the new ternary
In recent years, a strong research effort has been compound SrTiO3 was investigated. Like BaFel _xTaxO3,
made for developing oxygen sensors that work at high it shows a faster response time and presents a transition
temperatures. from the n-type to the p-type at low oxygen partial
The main reason for this is new legislation that pressure (for TiO2, this transition is observed at Po~ = 1
prescribes the control of the exhaust gases from internal atm [23]).
combustion engines. Moreover, SrTiO3 is characterized by different work-
In these engines, there is a simultaneous variation ing mechanisms in threePo~ ranges; in fact the parameter
of the partial pressure of oxygen and other gases when m changes from - 6 to - 4 with increasing Po~ and it
the air/fuel ratio is varied near the ignition point (lambda equals + 4 for Po~ = 1 atm [24].
point); for this reason, oxygen sensors devoted to this Semiconducting thin films with a conductance vari-
application are called lambda probes. ation due to surface effects were studied for detecting
Some semicondueting materials prepared for this low oxygen pressure (1-1000 mbar) at medium tem-
application are reported in Table l(a). At working peratures (673--873 K). In that case, there is no oxygen
temperatures, there is an equilibrium between the at- diffusion in the bulk. The oxygen chemisorption on the
mosphere surrounding the sensor and the bulk stoi- surface of polycrystalline thin films causes the formation
chiometry. of Schottky barriers among the grains; when the con-
The relation between the conductance and the oxygen dition Ld >Lc/2 is satisfied (Ld is the Debye length and
partial pressure is Lc is the crystalline size), complete depletion of grains
is obtained and the mobility is not thermally activated
tr= C exp( - E A/KT)Po21/m [25].
Table l(b) reports some examples of materials in-
Table 1
vestigated as oxygen sensors at low and medium tem-
Examples of materials investigated as oxygen lambda sensors in the peratures. These materials are highly sensitive to oxygen
form of a thin film (the minimum detectable concentration is 1 ppm), and
(a) Bulk-conductance types can also detect other gases that react with the previously
chemisorbed oxygen. Their use is therefore suggested
Material Oxygen Activation Temperature Reference together with other sensors in an array.
sensitivity energy (K)
(eV)
2.2. Detection of gas in air with semiconducting thin
TiO2 - 4, - 6 1.5 973-1073 7 films
TiOz(Nb, Cr) -4, -6 1273 8
SrTiO2 - 6, - 4, 1.24 973-1373 9 Metal oxides are the most investigated materials for
+4
gas detection, their working mechanism being the vari-
Ga203 - 4 1.9 1173-1273 10, 11, 12
CeO2 - 6, - 4 973--1373 13, 14 ation of surface conductance in the presence of a
BaTiOa(Nb) -4 13 gaseous atmosphere. Tin oxide is the most studied
material. Different metals and oxides are used as dopants
(b) Surface-conductance types or catalysts in order to enhance the response towards
some gases, the most important 'semiconductor-catalyst'
Material Temperature (K) References structures being presented in Table 2. Tin oxide modifies
the response spectrum to gases by suitable changes of
SnO2 573-773 16
SnO2(Li) 573-773 15
the dopant or the catalyst deposited.
SnO2/Pt 523-573 20 As can be inferred form Table 2, many authors report
ZnO 573-773 17, 18 different response spectra towards gases for the same
ZnO(Li) 673-773 19 semiconducting material. An explanation for this can
Cu20 21
be found either in the different working temperatures
Nb205 673 22
or in the local variations of the material structural
 G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109 105

Table 2 104
Non-exhaustive list of the studies performed on SnO 2 and on its (AG/G)%
dopants as gas-sensor materials
103 Y
Doping or Detectable gas References co
catalyst material z
102
- H2 26, 27, 30, 36, 43
Sb203, Au H2, H 2 S 28, 29 y
Sb, Pt H2 31 101
- H2, NO, H2S 32 f
- N O ` ` 33
Pd-Au NO.,, C2HsOH, C--all6 34 ]0 0 I , , , , , ,,,
- ethyl ether, halothane 35
100 1000 104
- C2HsOH, H2NH3, CO 37 Gas concentration(ppm)
- NO 2 38, 55
- H2S 39 Fig. 1. Gas sensitivity AG/Go to CO, CI-L and H2 vs. gas concentration
- CO 40, 41, 54, 57 at 723 K for an SnO2 (Bi203) thin film.
Pal, PdO CO 30, 42, 58
Pd, Pt H2, CO 44 Table 3
Pt C3H8, CO, H2, CH4 45 Non-exhaustive list of studies on semiconducting metal oxides (for
Pd, Pt, Au, Ni, W, Fe CH4, H~ 46 SnOz based thin films, see Table 2)
Pd hydrocarbons, H2C12 47
Pd CH2, 02, CHCI3, CCI4 47 Semiconductor Doping Detectable Refer-
- AsH3 48 material material gas ences
Pd CO, C2HsOH 49
- C2HsOH, CO, CsHa 50, 63 YBa2Cu307 _ 8 NO 66
Cd NO,, NO2, CO, H2, (24, 51 In203 03 67
HIo LnCoOs_x CO 68
Cd CH4 51 L n = N d , Sm, Eu, La
In NO 52 Co304 CO 69
- H2, n-C4Hm, C2HsOH 53 BixMoyOz alcohols, ketones, 70
Sb CO 57 H2, C O
Pt H2 56 CrLsTio.203 NH3 71
Pt HzS 59 ZnO A1203, In203 NH3, H2, CH4, 72, 73, 74
Bi203 H2 60, 61 C4H1~ C2H~OH
Co CO 62 acetone
ITO NO2, NO, CO, 73, 74
Cdln204 CO 57
In203 CeO2 O9 67
properties, which depend on the preparation param- Snl _~Fe~Oy CO, ethanol 75, 76, 77,
eters. An example can be represented by the different 78
clustering kinetics of the same catalyst layer on the
film surface.
The dimensions of crystallites in these films are
At constant partial pressure of oxygen and working estimated by means of XRD analysis and are between
temperature, the experimental dependence between the
5 and 13 nm; since we estimate that the Debye length
conductance and the partial pressure of a single gas
ranges between 3 and 5 nm, then grains with the lowest
is given by
dimensions should be completely depleted (flat-band
G = O0 + r(t',.s) m
situation) while grains with higher dimensions should
be only partially depleted (band-bending situation).
where Pg~ is the gas partial pressure and 3' is a constant A large number of binary and ternary oxides were
that depends on the material. prepared and characterized as gas sensors in order
Assuming that a monocrystalline layer is fully depleted improve the selectivity and the long-term stability. Table
of electrons and only one species of oxygen ionosorbed 3 reports some meaningful examples of thin films having
is active for gas detection, Windischmann and Mark a pronounced sensitivity towards different gases.
found in the case of CO that m = 0.5 [64]. The sensing properties of the ternary compound
These assumptions are not fully valid for polycrys- Snl_xFexOy will be examined in the next section.
talline thin films; in fact the response of an SnO2-Bi
sputtered film to 1000 ppm of H2, CO and CH4, reported 2.3. A.c. measurements
in Fig. 1, follows this relation with m = 1/3.
Details of the preparation of these sensors are re- The electrical responses of sensors reported in Tables
ported elsewhere [66]. 1-3 were obtained with current-voltage measurement
106
with a d.c. voltage supply. Recently, measurements were
made supplying the sensors with a.c. voltage. The
response spectrum to various gases varied according
to the supply frequency [79].
For example, Fig. 2 shows the sensitivity AR/Ro to
NO2 and CO at different frequencies for an SnO2-AI
thin film; for increasing frequencies the NO2 sensitivity
increases while the CO sensitivity remains constant.
Details of the sample preparation are reported else-
where [80]. The response kinetics to NO2 at three
supply frequencies of the same film are reported in
Fig. 3. It is possible to note the improvement of sensor
response at 100 kHz. Since the sensor impedance is
the sum of contacts, grain and grain-boundary contri-
butions (each is a resistance and capacitance in parallel),
a.c. measurements allow us to gain information about
the impedance spectrum of each contribution and to
calculate the equivalent circuit of the sensors. Therefore,
it is possible to obtain information from impedance
spectroscopy for understanding the sensing mechanism
for each single gas. Moreover, since the sensor response
changes with the frequency, it is possible to obtain a
selective detection of gases by fast sweeping of a single
sensor at different frequencies.
1000
T=573K
100
•~ 10
i 1
0 t i i LliJi I ........
lOO lOOO
f (Hz)
Fig. 2, Gas sensitivity vs. supply frequency of an SnO2 (A!203) thin
film grown with the RGTO technique.
18 ppm NO 2
T=573 K
10-6
Re(Y(s)) ~ ~
10n
10-8
10-9
10do
0 500 1000
Fig. 3. Response kinetics to NO2 for three different frequencies of
the s a m e S n O 2 - A l 2 0 3 thin film.
G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109
3. New preparation techniques for gas sensors
3.1. Multilayered gas sensors
The control of electronic and structural properties
of materials is important for modifying the response
spectrum towards gases and the long-term stability. An
interesting approach is represented by the preparation
of semiconducting multilayers.
This technique was first proposed in 1982 [81]; it
allows either the modulation of the material structure
or the modification of its catalytic activity; in fact the
gas-semiconductor interface is controlled by the outer
layer.
Careful attention should be paid to the selection of
the oxides that should form the multilayer. In fact, if
a compound with a low diffusion coefficient is chosen,
mixed oxide compounds are formed at the interface
of each layer, with a worsening of the sensing properties
and the long-term stability of the device.
For example, SnO2-aFe203 multilayers, grown by
CVD, are characterized by mixed oxide compounds at
the interface of each layer [78]. CdO deposited onto
an SnO2 layer is a multilayer with stable structure;
details of the preparation are reported elsewhere [51].
i
The spectral response of different films is reported in
18 ppm NO2 Fig. 4, which indicates the catalytic activity of the
cadmium oxide.
A further improvement in this technique should allow
us to obtain the controlled formation of mixed phases
and crystalline dimensions with an improvement of
selectivity and stability.
500 ppm CO
i . . . . . . . .
3.2. The RGTO technique
1o4 1o'
This technique, called by the author rheotaxial growth
and thermal oxidation, allows thin films to be prepared
with a high surface area and crystallites with nanometric
size.
1200
1ooo ~ 1 0 0 ppm NO x
100 Hz
1 KHz 800 " b)
600
400
2OO
o , ' ' l ' ' ' i ' ' ' i ' ' ' l ' ' '
0 20 40 60 80 100
1500 2000 2500 Cd thickness (,~)
t(s)
Fig. 4. NO2 sensitivity of the bilayer SnOz-CdO vs. the thickness of
Cd deposited onto the tin oxide and successively oxidized at 773 K.
The working temperature was: (a) 523 K; (b) 573 K.
 G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109
This technique was used to prepare tin oxide and
mixed oxides like Snl _xFeOy or SnOz-ml203, first grow-
ing the metallic alloy and transforming it into an oxide
compound [77,78].
For mixed oxides, the metallic alloy was deposited
onto the substrate at a temperature higher than the
alloy melting point; the film surface presented the
morphology reported in Fig. 5.
The surface morphology after the thermal cycle that
transforms the metal into an oxide is reported in Fig.
6. The responses to CO for SnO2 and Snl_xFeOy are
both reported in Fig. 7 of Ref. [77]. Note that the
ternary compound shows a better sensitivity towards
CO with respect to tin oxide.
The ternary oxide presents a long-term stability; in
fact, the conductance Go at 573 K varied by 4% over
a period of three months.
Fig. 5. SEM micrograph of the metallic Sn-Fe film deposited at 806
K.
Fig. 6. SEM micrograph of the thin film reported in Fig. 5 after
thermal oxidation.
107
4. Conclusions
The development of gas sensors in the form of thin
films is justified for technological reasons. In fact it is
possible to prepare devices with small size and low
power consumption which can easily be integrated in
an array. Tin oxide is the most investigated material
and presents the most satisfactory characteristics for
gas detection, but a research effort should be done to
improve the knowledge of its working mechanisms and
the long-term stability.
Other materials are also promising for gas detection.
Device arrays can be formed with different semicon-
ducting materials, with a suitable tailoring of the re-
sponse spectrum [5].
Thin films with bulk effects are satisfactory sensors
for oxygen at high temperature, but their stability in
the exhaust gas of engines should be improved [9,10].
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