Sensors and Actuators B 59 Ž1999.

210–215
www.elsevier.nlrlocatersensorb

Electrical properties under polluting gas žCO / of Pt- and Pd-doped

polycrystalline SnO 2 thin films: analysis of the metal aggregate size
effect
a,)
I. Matko , M. Gaidi a , J.L. Hazemann b, B. Chenevier a , M. Labeau a

a
´
Laboratoire des Materiaux ´ Physique, Institut National Polytechnique de Grenoble, UMR 5628 CNRS, BP 46, F-38402 Saint-Martin d’Heres
et du Genie `
Cedex, France
b
´
Laboratoire de Geophysique Interne et Tectonophysique, URA 733, BP 53, F-38041 Grenoble Cedex, France

Abstract

In Pt- or Pd-doped SnO 2 thin films prepared by using a submicronic aerosol pyrolysis method where both metal elements are
co-deposited, the best sensitivity to CO is obtained from low-concentration PdrPt precursor solutions. TEM observations from SnO 2 thin
films doped with small amounts of platinum have been combined with results obtained from in situ X-ray Absorption Spectroscopy
ŽXAS. to give a schematic description of the metallic particle effect on the electrical properties of the films. It is demonstrated that the
lower the concentration, the smaller are the metallic particles. The evolution of the particle size and density as a function of concentration
can be understood in terms of nucleation-growth processes. The XAS analysis shows, in particular, that the Pt local environments are
modified by metal concentration variations and by the gas in contact with the film surface. The modifications are discussed on the basis of
competing bulk and surface contributions to CO reduction processes, the latter being dominant in smaller particles. It is inferred that
smaller particles contribute as a whole to the electrical behavior whereas in bigger particles, a surface and a bulk contribution have to be
considered. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: SnO 2 thin films; Sensitivity to CO; TEM; X-ray absorption spectroscopy ŽXAS.

1. Introduction conductance under pure air. and selectivity can be im-

proved w1–3x Žsee also Fig. 1.. For example, in Pt- and
Advances in solid material synthesis and new possibili-
Pd-doped SnO 2 thin films prepared by using a submicronic
ties offered by microtechnologies have contributed widely
aerosol pyrolysis method ŽPyrosol process. at a tempera-
to the development of devices for detecting polluting gases
ture of 5208C w4–6x, a maximum in sensitivity to CO is
in air, particularly reducing gases such as carbon monoxide
obtained for a metal concentration wPt or PdxrwSnx in the
and methane.
precursor solution close to 3% Žcf. Fig. 2.. It is possible to
Semiconductor sensors have been the subject of exten-
correlate the concentrations in the solution to film concen-
sive research and development as devices for the detection
trations by performing electron probe microanalysis from
of these toxic gases and for monitoring low levels of
the films ŽFig. 3.. For brevity in the following, the samples
gaseous components. SnO 2 is often used as an active
will be named by reference to the additive concentrations
element and may be fabricated using thin film technolo-
in the solution.
gies. It interacts with reducing gases by surface adsorption
Recent X-ray Absorption Spectroscopy ŽXAS. experi-
leading to an increase of the free electron density on the
ments performed at the Pt L III edge have shown that in
surface and ultimately to an enhanced electrical conduc-
Pt-doped SnO 2 thin films, initially oxidized Pt particles
tance. By dispersing a low concentration of small metallic
can be reduced if the film surface is put in contact with air
particles Žpalladium, platinum, copper . . . . on the surface
containing small amounts of CO gas w7,8x. In particular,
of the SnO 2 grains, the sensitivity Ždefined as S s Ž s y
XAS data have shown that 3% Pt-doped films exhibit the
s 0 .rŽ s 0 ., s : conductance under gas pollutant and s 0 :
highest oxidation tendency of the Pt particles. They have
also given strong indications of an alteration in the metal-
)
Corresponding author lic particle local environment density as a function of

0925-4005r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 Ž 9 9 . 0 0 2 2 2 - 1
 I. Matko et al.r Sensors and Actuators B 59 (1999) 210–215 211

Fig. 1. Sensivity of 3% Pt- and Pd-doped SnO 2 thin films exposed to air
mixed with 300 ppm of CO gas as a function of temperature. In this Fig. 3. Pt to Sn concentration ratio ŽConc. F . in the the film as a function
temperature range, pure SnO 2 thin films exhibit a sensitivity smaller than of the corresponding concentration in the precursor solution ŽConc. S ..
5.

metal concentration: in samples obtained from Pt low
concentration, first neighbor environments are made of a
limited number of atoms and this number increases if more
Pt precusor is added into the solution Žsee Table 1..
Additionally, XAS data have shown that for low metal
concentration in the precursor solutions, metal particle
particles in the films are smaller. A complete description
of the XAS analysis and the interpretation of the electrical
properties can be found in Ref. w7x.
To further analyze the metal particle size distributions,
a Transmission Electron Microscopy ŽTEM. analysis of
the film microstructure has been performed. In this paper,
results from TEM observations of the density, size distri-
bution of the Pt particles are combined with partial results
from XAS to correlate the metal concentration in the films
with the density and the particle size distribution. The
ultimate goal of the study is to propose a schematic
description of the relations between these parameters and
the electrical behavior of the films.
2. Experimental details
A series of pure SnO 2 thin films as well as films SnO 2
doped with Pt have been deposited on 500 mm thick
silicon substrates using a Pyrosol co-deposition method
w4,5x. The platinum content in the precursor solution was 3,
6, 8, and 12 at.%. The synthesis conditions Žthe constant
gas flow, the temperature 5208C and time 20 min. have
been kept constant throughout the series.
TEM specimen have been prepared in plane view mode
to allow countings of particles to be made on wide areas.
Specimen for perpendicular cross-section observations have

Table 1
Evolution of the Pt local environments in Pt-doped SnO 2 thin films. Total
numbers of next-neighbor atoms are given in bold–italic font
Pt concentration Gas 1st Distance Number
Žat.%. mixture neighbor ˚.
ŽA
6 Air O 1.96 4
4
6 N2 q900 C 1.89 1.97
ppm CO O 2.03 2.32
Pt 2.48 0.90
5.19
Fig. 2. Sensivity determined at T s 508C of Pt- and Pd-doped SnO 2 thin 12 Air or N2 q900 O 1.96 3.73
films exposed to air mixed with 300 ppm of CO gas as a function of ppm CO Pt 2.73 3.81
metallic element concentration in the precursor solution ŽConc. S .. The 7.54
sensitivity value of 1% Pt-doped films has been obtained from Ref. w6x.
212 I. Matko et al.r Sensors and Actuators B 59 (1999) 210–215
also been prepared to check the possible existence of
inhomogeneities in the particle distribution from the sub-
strate to the film free surface. A classical preparation
method including first a mechanical polishing followed by
ion-milling has been used. For plane view mode observa-
tions, the final thinning of samples from 50 mm down to
transparency to electron beam was performed using a
Baltech ion-milling machine. One side milling from the
substrate side was used with ion beam acceleration voltage
5 kV, ion beam current 2 mA and incidence angle 158. For
cross-section specimens, a double-side ion milling was
done with ion beam acceleration voltage 5 kV, ion beam
current 1 mA and incidence angle 128. The sample was
oscillated during milling, the plane of deposited layers was
oscillating by "308 around the direction perpendicular to
incident beam.
The TEM observations have been performed on a JEOL
200 CX. Obtained negatives for plane view observations
have first been scanned and results were then transferred to
a Macintosh PowerPC computer. The determination of the
Pt aggregate grain-size statistics has been performed with
assistance of the public domain NIH Image program w9x.
Fig. 4. TEM image and corresponding electron diffraction pattern from an 8 at.% Pt-doped SnO 2 film.
3. Results and discussion
All TEM micrographs exhibit contrast variations such
as those of the typical TEM image of Fig. 4, recorded from
an 8% Pt-doped sample. The contrast indicates the pres-
ence of two grain types:
Ži. large grains frequently facetted, with a grain-size
varying in the range of 10–30 nm and filling most of the
image areas,
Žii. smaller grains scattered all over the images.
The fact that larger particles are SnO 2 grains was
checked from the electron diffraction pattern given in Fig.
4. All observed diffraction rings can be indexed using
tetragonal SnO 2 cell-parameters, with rutile structure-type
Žspace group P4 2rmnm.. The expected positions of the Pt
two smallest rings are also shown, but neither the 111 ring
too close to SnO 2 111 neither the 200 ring could be
detected. This indicates that for all investigated composi-
tions, the metal particles are too scattered and too small to
contribute a significant diffraction signal.
For aggregate density measurements, 100 = 150 nm2
areas have been investigated on TEM micrographs. In the
 I. Matko et al.r Sensors and Actuators B 59 (1999) 210–215 213

then selected according to their position with respect to

this threshold. A simple use of this technique is neverthe-
less difficult as various contrast levels are present in the
micrographs. Instead of it, a first step of analysis was
made by attributing a dark contrast to small and round-
shape areas suspected to be platinum particle images.
These dark areas have then be processed using some
particle analysis functions available in NIH and the results
plotted as grain-size distribution histograms. The particle
density is minimum for 3% Pt concentrations, increases to
a maximum value of 27 P 10 3 particles mmy2 and then
saturates. Bar charts of size distributions are given in Fig.
5. From these charts, a weighted mean-size Ž² s :. has been
obtained and the variations as a function of Pt concentra-
tion plotted in Fig. 6. ² s : is minimum at the lowest Pt
concentrations and then begins to increase. Although ² s :
variations are weak in the lowest concentration regions, a
further examination of the distributions ŽFig. 5. show that
the proportions of the particle diameters smaller than 1.5
nm decrease with increasing the concentrations. No ten-
dency to saturation is detected in the mean-size evolution.
Density and grain-size evolution can be understood in
terms of nucleation and growth processes: from an initial
situation where particles are very small Žthe mean-size is
smaller than 2 nm for 3% Pt concentration., density and
size both increase up to a maximum density value from
where it saturates. For Pt concentration higher than 8%,
the density is kept constant, nucleation sites are all occu-
pied and the additional Pt atoms agglomerate to already
existing particles, making them bigger.
Film thickness estimations from TEM images in the
perpendicular cross-section mode revealed a significant
dependence on platinum content. The film thickness very
sharply decreases to a third of its initial value, with

Fig. 5. Grain-size distribution of Pt particles as a function Pt content in

the precursor solution.

perpendicular cross-section mode, the observations re-

vealed a good homogeneity of the small particle distribu-
tion along the normal direction. As all micrographs exhibit
a similar contrast, the various investigated regions have
been supposed to be of the same thickness. These consid-
erations make possible the discussion of the density in
terms of surface density.
To determine the surface density and size distribution of
the very small metallic nanoparticles, particles have been
counted and sorted according to their size. NIH image Fig. 6. Pt grain-size and density as a function of concentration in the
processing requires a threshold to be defined and areas are precursor solution ŽConc. S ..
214 I. Matko et al.r Sensors and Actuators B 59 (1999) 210–215
Fig. 7. Pt concentration dependence of the film thickness.
increasing Pt concentration, suggesting that the growth-rate
is strongly altered by the platinum incorporation in the
film ŽFig. 7..
In Table 1, and more specifically in the case of 6% and
12% Pt-doped films exposed to air, the density of the next
neighbor shell of a central Pt atom obtained from XAS
data changes from 4 to 7.5, respectively. In small particles,
the surface contribution to the total energy is great and to
minimize it, modifications of the local environments usu-
ally observed in bulk material may occur. In particular, the
local environment density is lowered by the rearrange-
ments at the surface. Our XAS results are supported by an
interpretation of this type. Another important result ob-
tained from the XAS study is the change in the chemical
species contributing to the Pt surrounding when either the
Pt concentration or the gas mixture is varied. This can also
be understood in terms of a change in the contribution of
the surface to bulk ratio to the reductionroxidation pro-
cesses: for 6% Pt concentrations, i.e., for small Pt parti-
cles, a large fraction of the particle is oxidised if the film is
exposed to air. A reduced state characterized by the reduc-
tion in the O number and the existence of C and Pt atoms
in the surrounding is obtained by contact with CO. For
12% concentration, i.e., for bigger particles the proportion
of Pt in the surrounding is even larger whatever the gas
mixture and the O proportion is further reduced. As in the
bigger particles, the core contributes predominantly to the
XAS signal and is also more difficult to oxidize, this
demonstrates a surface and a core contribution to the Pt
reductionroxidation.
Analysis of the TEM observations combined with XAS
results allows then to propose a temptative description of
the size and density effect of the Pt aggregates on the
electrical properties of SnO 2 thin films. For small Pt
concentrations in the precursor solution, low densities of
very small particles — with some size distribution how-
ever — are dispersed in the film. For the smallest ones,
the whole particle is concerned with reductionroxidation
processes and participates in the injection of electrons in
the depletion zone of SnO 2 grains. If the precursor con-
tains more Pt, this results in bigger particles and the
density tends to saturate. Bigger particles have then to be
viewed as a sum of long radius surface shell and a core: in
this assumption, the surface contributes to the electron
injection only at the contact areas with SnO 2 and the core
only marginally takes part to it.
From this analysis and additionally from XAS results
w7,8x that have shown 3% Pt-doped films exhibit the
highest oxidation tendency of the Pt particles, it clearly
appears that a probably much better sensitivity would be
achieved if the aggregate distribution in the film could be
specifically characterized by a very small particle size
coupled with a high density. This improvement has cer-
tainly to be sought by optimising deposition parameters as
reported in Refs. w10–15x.
4. Conclusions
TEM observations from SnO 2 thin films doped with
small amounts of platinum have been combined with
results obtained from in situ XAS to give a schematic
description of the metallic particle effect on the electrical
properties of the films. It is demonstrated that the lower
the concentration, the smaller are the metallic particles.
The evolution of the particle size and density as a function
of concentration, can be understood in terms of
nucleation-growth processes. The XAS analysis shows, in
particular, that the Pt local environments are modified by
metal concentration variations and by the gas in contact
with the film surface. The environment modifications and
their consequences on the electrical sensitivity of the films
have been discussed on the basis of competing bulk and
surface contributions to CO oxidation processes, the latter
being dominant in smaller particles. It is inferred that
smaller particles contribute as a whole to the electrical
behaviour whereas in bigger particles, a surface and bulk
contribution have to be considered.
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Dr. Igor Matko, presently post-doc fellow at the LMGP, has obtained his
PhD thesis in the field of Solid State Physics at the Department of Metal
Physics, Institute of Physics, Slovak Academy of Sciences ŽSlovak
Republic. in 1997. He is expert in methods for microstructural characteri-
zation, as well as kinetics analysis of phase transformations in solids.
Mounir Gaidi, graduated at Monastir University of Science ŽTunisia. in
1995 ŽMaster in Chemistry and Physics., started in 1996 a PhD thesis
work in Material Physics at the LMGP on the ‘‘Structure and Electronic
State of Metallic Aggregates in Semi-Conducting SnO 2 Thin Films Used
as Pollutant Gas Sensors’’. He has acquired a good expertise in the
optimisation of sensor properties by manipulating the concentrations of
metallic nanoparticles added in SnO 2 films.
Dr. Jean-louis Hazemann is head of the EXAFS Station on the Beam line
project ‘‘IF’’ at the European Synchrotron Radiation Facility ŽESRF.,
Doctor in Material Science. He has been involved for 7 years in syn-
chrotron instrumentation. Chief of the EXAFS Station, he has been in
charge of the development of the scientific activity on various uses of the
XAS in the frame of the programme of structural investigation on
disordered materials in environmental problems.
Dr. Bernard Chenevier, Senior Scientist, Doctor of Physics Science, has
strong expertise in microstructural and physical properties analysis of thin
films. He has been responsible for LMGP partnership in several national
and international programs.
Pr. Michel Labeau is a Professor in Material Sciences, Doctor of Physics
Science, with 23 years experience of research in material sciences,
including thin films synthesis of semiconductor for gas applications. He is
head of the ‘‘Films for Components and Sensors’’ Group of LMGP. He is
responsible for several national and international cooperation programs.