A NOVEL GAS SENSOR FOR HYDRO-

CARBONS DETECTION BASED ON

POROUS SILICON PERMEATED WITH
Sn-V MIXED OXIDES

R. Angelucci, A. Poggi, C. Critelli1, L. Dori, F. Cavani1,

A. Parisini, A. Garulli, G.C. Cardinali and M. Fiorini
CNR LAMEL - Institute, via Gobetti 101, 40129 Bologna - Italy
1
Dipartimento di Chimica Industriale e dei Materiali,
viale Risorgimento 4, 40136 Bologna - Italy

Abstract
The characteristics of an innovative chemical gas sensor
device made of a macroporous silicon substrate hosting a thin
layer of Sn-V mixed oxides are presented. A wet permeation
technique has been used to induce co-precipitation of V and
Sn oxohydrates providing a conformal coverage of the
macroporous structure by the thin sensing film. The grain size
and the chemical composition of the Sn-V polycrystalline oxide
layer have been investigated and the experimental data are
reported. Moreover, results on the sensitivity of a Sn-O-V
permeated porous silicon device to C6H6, CH3OH and CO
gases are shown and compared.

1 Introduction
To enhance gas sensor performance in terms of sensitivity, selectivity and
reliability, sensor array, advanced techniques for signal processing and, in some
case, monolithic integration with relevant electronic circuits have been proposed.
To fully exploit the high potential of this approach, sensor substrates and sensor
fabrication processes compatible with Si microelectronic technologies are
extremely important. Following these requirements and with the aim to realize
advanced microsensors for monitoring very low concentration of pollutant species
such aromatic hydrocarbons, in this paper a macroporous silicon substrate hosting
a thin layer of Sn-V mixed oxides is presented as a novel gas sensor device. The
choice of a macroporous Si substrate and of tin-vanadium mixed oxides has been
based on the peculiarity of the high specific surface area of the anodized Si
substrate and on the proved catalytic properties towards hydrocarbons of the used
chemical compounds [1], respectively. To provide a conformable and uniform
coating of the macroporous Si structure with a thin sensing layer, a wet permeation
technique has been used to induce co-precipitation of V and Sn oxohydrates. In
this work, experimental data on the conformal coverage of the macroporous
structure by the thin film, the grain size and the chemical composition of the Sn-V
polycrystalline oxide layer are reported. Moreover, results on the sensitivity of a
Sn-O-V permeated porous silicon device to C6H6, CH3OH and CO gases are
shown.

2 Results and discussion

The macroporous silicon layer has been shaped on n+/n substrate; a
detailed description of the sample preparation has been already reported in [2].
The PS surface shows a honey comb-like structure with a nearly square section of
the pores and an average side dimension of about 300 nm. A continous silicon
dioxide film on PS provide a good insulation between the substrate and the
sensing layer. Cross-sectional TEM observations of the permeated PS sample
show the presence of a polycrystalline thin film on the SiO2 layer covering the
macroporous walls. An investigation of the film composition by electron diffraction
has uniquely revealed a SnO2 phase with the cassiterite structure. The size and
the lattice structure of the grains have been investigated by High Resolution
Electron Microscopy (HREM). The grain size of the SnO2 crystallites has been
found to range from 3 to 10 nm as shown in the HREM micrograph reported in
Fig. 1. No evidence of crystalline V-oxydes has been detected.
Fourier Transform Infra-Red (FTIR) spectrum of Sn-O-V permeated PS sample is
reported in Fig. 2: the typical absorption bands of crystalline V2O4 and V2O5 are not
observed, whereas an absorption at around 960 cm-1, typical of non-stoichiometric
vanadium suboxides, is evident. Therefore, from the FTIR analysis of the sensing
film and from the results of the TEM investigation we can infer that vanadium
should be present in the thin layer either as solute atoms in SnO2 microcrystal and
as VxOy amorphous suboxides. The presence of vanadium in the film has been
furtherly evaluated using the Energy Dispersive X-ray spectroscopy. The results
have highlighetd that vanadium is incorporated into the thin sensing layer
uniformely along the whole depth of the macroporous layer. From these results we
can conclude that the co-precipitation from an ethanolic solution containing Sn and
V precursor elements is a viable, cheap and powerful technique to provide a good
coverage of the macropore walls by a thin Sn-V-O layer. Furthermore, the
nanometric scale of the polycrystalline grains and the uniformity in the grain size
should be in favour of a better film conduction mechanism as well as of an
enhanced film sensitivity due to an increased number of activated centres. In
Fig. 3, the response of the Sn-O-V permeated PS device towards C6H6, CH3OH
and CO has been reported at relatively low sensor operating temperature (300
°C): the same concentration of different gases (150 ppm in dry syntethic air)
induces different conductance changes of the sensing layer. These results confirm
the reported selectivity of the Sn-V system towards hydrocarbons. Moreover, as it
is shown in Fig. 4 the permeated porous structure allows to detect low
concentration values of benzene down to 5 ppm in dry air. Taking into account the
potential benefits coming from the device optimization, we can conclude that the
permeation of oxidised macroporous silicon with Sn-V mixed oxides is a viable
approach to fabricate gas sensors with sensitivity and selectivity suitable to monitor
low concentration of aromatic hydrocarbons like benzene.

[1] Bordoni, F. Castellani, F. Cavani and F. Trifirò, J.Chem. Soc. Faraday Trans.,
90 (1994) 2981
[2] Angelucci, A. Poggi, L. Dori, G.C. Cardinali, A. Parisini, G. Pizzochero,
F. Trifirò, F. Cavani, C. Critelli, L. Boarino, Proc. E-MRS 1996 Spring Meeting-
Symposium L, Strasburg (France) June 4-7 1996.

Fig. 1: HREM micrograph of Sn-V mixed oxides observed in permeated PS structure.

 0,15

Fig. 2: FTIR spectrum of the Sn-V-O

permeated PS sample: the absorption

Absorbance (a.u.)
peak at 960 cm-1 is typical of non
0,10
stoichiometric vanadium oxides. The
other three absorption peaks are due to
SnO2.
0,05

0,00
1000 900 800 700 600 500 400
-1
wavenumber (cm )
0.030
Sn-V-O PERMEATED PS

Dry air
0.025
T = 300 °C
V=7V
Fig. 3: Conductance changes
Current ( µA)

0.020
due to separate exposures to

C6H6 (150 ppm)

150 ppm of C6H6, CH3OH,
0.015
CO (150 ppm) CO in dry air.
CH3OH (150 ppm)
0.010

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Time (s)

Sn-V-O PERMEATED PS
0.11
Benzene in dry air
0.10
T = 400 °C
V=8V

0.09
Fig. 4: Conductance changes
Current ( µA)

after flowing 50 and 5 ppm of 0.08

50 ppm
C6H6 in dry air. 0.07

0.06 5 ppm

0.05

2000 2500 3000 3500 4000 4500 5000

Time (s)