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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.
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 G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109
with a d.c. voltage supply. Recently, measurements were 3. New preparation techniques for gas sensors
made supplying the sensors with a.c. voltage. The
response spectrum to various gases varied according
3.1. Multilayered gas sensors
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 The control of electronic and structural properties
thin film; for increasing frequencies the NO2 sensitivity of materials is important for modifying the response
increases while the CO sensitivity remains constant. spectrum towards gases and the long-term stability. An
Details of the sample preparation are reported else- interesting approach is represented by the preparation
where [80]. The response kinetics to NO2 at three of semiconducting multilayers.
supply frequencies of the same film are reported in This technique was first proposed in 1982 [81]; it
Fig. 3. It is possible to note the improvement of sensor allows either the modulation of the material structure
response at 100 kHz. Since the sensor impedance is or the modification of its catalytic activity; in fact the
the sum of contacts, grain and grain-boundary contri- gas-semiconductor interface is controlled by the outer
butions (each is a resistance and capacitance in parallel), layer.
a.c. measurements allow us to gain information about Careful attention should be paid to the selection of
the impedance spectrum of each contribution and to the oxides that should form the multilayer. In fact, if
calculate the equivalent circuit of the sensors. Therefore, a compound with a low diffusion coefficient is chosen,
it is possible to obtain information from impedance mixed oxide compounds are formed at the interface
spectroscopy for understanding the sensing mechanism of each layer, with a worsening of the sensing properties
for each single gas. Moreover, since the sensor response and the long-term stability of the device.
changes with the frequency, it is possible to obtain a For example, SnO2-aFe203 multilayers, grown by
selective detection of gases by fast sweeping of a single CVD, are characterized by mixed oxide compounds at
sensor at different frequencies. 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].
1000 i
The spectral response of different films is reported in
T=573K 18 ppm NO2 Fig. 4, which indicates the catalytic activity of the
100
cadmium oxide.
A further improvement in this technique should allow
us to obtain the controlled formation of mixed phases
•~ 10
and crystalline dimensions with an improvement of
selectivity and stability.
500 ppm CO
i 1
0 t i i LliJi I ........ i . . . . . . . .
3.2. The RGTO technique
lOO lOOO 1o4 1o'
f (Hz)
This technique, called by the author rheotaxial growth
Fig. 2, Gas sensitivity vs. supply frequency of an SnO2 (A!203) thin
film grown with the RGTO technique. and thermal oxidation, allows thin films to be prepared
with a high surface area and crystallites with nanometric
size.
18 ppm NO 2 1200
T=573 K
10-6 1ooo ~ 1 0 0 ppm NO x
100 Hz
Re(Y(s)) ~ ~ 1 KHz 800 " b)
10n
600
10-8 400
2OO
10-9
o , ' ' l ' ' ' i ' ' ' i ' ' ' l ' ' '
0 20 40 60 80 100
10do
0 500 1000 1500 2000 2500 Cd thickness (,~)
t(s)
Fig. 4. NO2 sensitivity of the bilayer SnOz-CdO vs. the thickness of
Fig. 3. Response kinetics to NO2 for three different frequencies of Cd deposited onto the tin oxide and successively oxidized at 773 K.
the s a m e S n O 2 - A l 2 0 3 thin film. The working temperature was: (a) 523 K; (b) 573 K.
G. Sberveglieri / Sensors and Actuators B 23 (1995) 103-109 107
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