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Thin Solid Films 518 (2009) 1109–1113

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Thin Solid Films


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

The effect of Au and Pt nanoclusters on the structural and hydrogen sensing


properties of SnO2 thin films
I. Fasaki a, M. Suchea b, G. Mousdis a,⁎, G. Kiriakidis c, M. Kompitsas a
a
National Hellenic Research Foundation, Theoretical and Physical Chemistry Institute, Vasileos Konstantinou Ave. 48, 11635 Athens, Greece
b
IESL-FORTH and University of Crete, Chemistry Dept., P.O. Box 1385, Voutes, 71110 Heraklion, Greece
c
IESL-FORTH and University of Crete, Physics Dept., P.O. Box 1385, Voutes, 71110 Heraklion, Greece

a r t i c l e i n f o a b s t r a c t

Available online 11 August 2009 Au and Pt nanoparticle modified SnO2 thin films were prepared by the sol–gel method on glass substrates
targeting sensing applications. Structural and morphological properties of these films were studied using X-
Keywords: ray Diffraction and Scanning Electron Microscopy. It was proved that the films crystallized in tetragonal
SnO2 rutile SnO2 crystalline structure. Scanning Electron Microscopy observations showed that the metallic
Nanoparticle modification clusters' dimensions and geometry depend on the kind of the metal (Au or Pt) while SnO2 films surface
Hydrogen sensing
remains almost the same: nanostructured granular very smooth. Optical properties of the films were studied
using UV–visible spectroscopy. The modified SnO2 films were tested as hydrogen sensors. The response of
SnO2, SnO2–Au and SnO2–Pt thin films against hydrogen was investigated at different operating
temperatures and for different gas concentrations. The addition of metal nanoparticles was found to
decrease the detection limit and the operating temperature (from 180 °C to 85 °C), while increasing the
sensing response signal.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction be grown. The implantation of the metals increased the sensitivity and
the selectivity towards many gases.
Hydrogen is an abundant, renewable, efficient, clean energy The detection of hydrogen using SnO2 thin films enhanced with Pt
source. As an industrial gas, it is currently used in a large number of or Au nanoparticles has been scarcely studied [15,16]. Nomura et al.
areas, e.g., chemistry (crude oil refining, plastics, as a reducing reported the detection of 1000 ppm hydrogen at operating tempera-
environment in float glass industry, etc.), food products (hydrogena- tures of 150–500 °C and the increase of the sensitivity and selectivity
tion of oils and fats), semiconductors (as a processing gas in thin film due to the implantation of gold (or iron) ions. Safonova et al. studied
deposition and annealing atmospheres) and transportation (as fuel in the Pt modification, among other metals, of SnO2 thin films and the
fuel cells and space vehicle rockets). influence on sensing of 10,000 ppm of hydrogen at 380 °C. Further-
All these applications require the development of hydrogen more, the detection of 1250–10,000 ppm of hydrogen was possible at
sensing devices that allow safe control of the gas usage. Devices the temperature range of 200–600 °C by a Pt/SnO2 Schottky diode
capable of detecting hydrogen presence below the lowest explosion [17].
limit (LEL) at 40,000 ppm have become indispensable to prevent In the present study the sol–gel method has been used to prepare
explosions [1]. SnO2 thin films unmodified and modified with Au and Pt nanopar-
Gas sensors based on metal oxide sensitive layers are playing an ticles. The structural and morphological properties of the films were
important role in the detection of toxic pollutants and inflammable analyzed and the samples were tested as hydrogen sensors. The
gases. Metal oxides and especially tin dioxide are widely used as basic operating sensing temperature was below 180 °C without significant
materials for the preparation of gas sensing devices operating in these sacrifice of sensitivity.
applications [2–4]. The effect of the addition of noble metallic particles,
such as Pt and Au, in tin oxide thin films on the gas sensing properties 2. Experimental
has been previously studied, mostly concerning the detection of
carbon monoxide, methane and nitrogen dioxide [5–14]. In most of The substrates (microscope glass slides) were cleaned by soaking
the cases, the materials were prepared by a chemical method for 24 h in a sulfochromic mixture and kept in isopropanol until used.
[5,9,10,12,13] knowing that low cost and easy prepared samples can A HAuCl4 solution in ethanol was prepared by dissolving Au in HNO3
3HCl then dried under vacuum and the remaining yellow crystals of
⁎ Corresponding author. Tel.: + 30 2107273838. HAuCl4 dissolved in ethanol to obtain a 0.3 M solution. The same
E-mail address: gmousdis@eie.gr (G. Mousdis). method was used to prepare a 0.3 M H2PtCl6 ethanolic solution. The

0040-6090/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2009.07.192
1110 I. Fasaki et al. / Thin Solid Films 518 (2009) 1109–1113

tin alkoxide starting solution was obtained from pure SnCl4 using the
gas NH3 method [18]. 1.73 ml of SnCl4 was added at 25 ml of dry
isopropanol under N2. To the above solution gaseous NH3 was bubbled
to form immediately a white precipitate. When the reaction was over
(no more precipitate) N2 was bubbled to remove the excess NH3. The
mixture was centrifuged to separate the precipitate from the liquid
diluted to 25 ml with dry isopropanol to give a 0.3 M Tin
(isopropoxide)4 solution in isopropanol. The working solution was
prepared by mixing the tin alkoxide starting solution with the HAuCl4
solution (or H2PtCl6 solution). The concentration of the metals (Au
and Pt) in the SnO2 matrix is 5 wt.%. The solution obtained was aged by
stirring at room temperature (R.T.) for 24 h. After spinning, tin oxide
gel films were dried at R.T. for 24 h and then heat-treated for 2 h at
510 °C in air. The thickness of the films was 96 (±6) nm, as measured
with an alpha step profilometer.
The films were characterized by Thermogravimetric Analysis
(TGA), Scanning Electron Microscopy (SEM) and X-ray Diffraction
(XRD). Additionally, the optical absorbance and the reflectivity were
measured. The optical transmittance spectrum was recorded using a Fig. 1. TGA of SnO2-Au thin film.
Varian Cary 50 UV/visible spectrophotometer in the wavelength range
of 200–1100 nm. In order to determine the crystalline structure of the
deposited films, X-ray diffraction (XRD) was performed using a quantitative evaluation was possible. Based on the same considera-
Rigaku diffractometer with CuKα X-rays. All films were characterized tions, the peaks at about 33° for Au and ~46° for Pt modified SnO2
using 2θ/θ geometry in angular range from 20 to 80° using a scan rate films were not indexed but they can be qualitatively attributed to the
0.02°/s. The corresponding diffractograms were compared with XRD metal presence onto surfaces.
diffraction patterns of tetragonal rutile SnO2 crystalline powder (JCPD Regarding Scanning Electron Microscopy (SEM) characterization,
No. 21-1250), in order to identify the crystallographic orientations all samples show the presence of a granular structured film of SnO2
which contribute to the diffraction patterns. with randomly distributed shaped particles on the surface. In the case
Hydrogen sensing tests were performed in an aluminum vacuum
test chamber. The chamber was evacuated down to 1 Pa, filled with
dry air at atmospheric pressure. The SnO2, SnO2–Au and SnO2–Pt thin
films were tested in the temperature range of 85–180 °C at hydrogen
concentrations from 10,000 to 500 ppm. The hydrogen concentration
was calculated on the basis on the partial pressures of the sensing gas
and air inside the chamber. A bias of 1 V was applied, and the current
through the film was recorded with a Keithley Mo. 485 Picoammeter.
Current modifications helped to monitor the hydrogen sensing in real
time. Sensitivity was defined as:

Ig −I0 R0 −Rg
S= =
I0 Rg

where R0 is the resistance of the film in air and Rg is the resistance of


the film in the gas/air mixture.

3. Results and discussion

3.1. Structural and morphological properties

The Thermogravimetric Analysis showed that the isopropanol and


the water evaporate at 118 °C while the remaining organics are
burned up to 400 °C. At 400 °C the HAuCl4 is reduced to metallic Au.
Over 500 °C there was no loss of mass (Fig. 1). A similar behavior was
observed for SnO2–Pt.
XRD characterization of films revealed that both kinds of samples
are polycrystalline SnO2 thin films with tetragonal rutile structure as
can be seen in Fig. 2. The presence of Au and Pt clusters onto films
surfaces seems to induce some change in film texturing tendency. For
instance, SnO2–Au films characterization by XRD has shown that they
are polycrystalline with a clear tendency of texturing in the [101] and
[200] crystalline directions of the tetragonal rutile structure as shown
in Fig. 2a. Corresponding results on SnO2–Pt films have shown
(Fig. 2b) a weaker tendency for texturing with a preferred orientation
towards the [200]. For both types of films X-ray diffractograms show
low intensity signals in the order of only few hundred counts com-
parable with background noise intensities. Due to this no further Fig. 2. XRD of SnO2–Au a) and SnO2–Pt b).
I. Fasaki et al. / Thin Solid Films 518 (2009) 1109–1113 1111

of the SnO2–Au sample, ignoring the quite big features of µm


dimensions attributed to dust formation and impurities while sample
preparation for SEM, the top particles are the most irregular shaped
with dimensions of few hundreds of nanometers, as shown in Fig. 3.
In the case of samples SnO2–Pt, the top features are clearly
hexagonal faceted. The dimensional distribution seems to be more
homogeneous as visible in Fig. 4.

3.2. Optical properties

In Fig. 5 the absorption and reflectance spectra of SnO2–Pt and


SnO2–Au thin films can be seen. As for the SnO2–Au sample, the
presence of Au nanoparticles is also confirmed by the peak at 560 nm
in the absorption spectrum, the surface plasmon resonance (SPR),
which is in consistence to the literature [19]. There was no evidence
for SPR attributed to Pt, therefore we assume that it is not in the Fig. 4. SEM image of the SnO2–Pt thin film.
recorded wavelength range.

3.3. Hydrogen sensing sensors towards hydrogen sharply increased with the increase of gas
concentration. For the same gas concentration, the response of SnO2–
The effect of Au and Pt nanoparticles on hydrogen sensing Au sensor towards hydrogen increased with the increase of operating
properties (operating temperature and sensitivity) was examined. temperature from 85 to 185 °C. Thus the Pt and in particular Au
SnO2 films, without metal nanoparticles, did not respond at all at presence in SnO2 films had a distinct influence on their response
temperatures lower than 180 °C and at concentrations lower than towards hydrogen at concentrations as low as 500 ppm.
5000 ppm (Fig. 6A). At 180 °C the SnO2 films have shown a relative Tin dioxide is known to be an n-type semiconductor. In this type of
response of about an order of magnitude therefore, this was enhanced semiconductors, the atmospheric oxygen adsorption may remove
distinctly by the presence of Pt in the SnO2–Pt modified films (Fig. 6B). electrons from the conduction band, resulting in the formation of
More than that, in the presence of Au the sensor response exhibited a
dramatic increase by 50 times at the same operating temperature
(Fig. 6C). Furthermore, the SnO2–Au sensor response could be
measured at even lower operating temperatures. Fig. 6D and E
shows these typical sensor signal curves towards hydrogen at the
operating temperatures of 150 and 85 °C respectively. It is clear that
the sensitivity of all SnO2 sensors towards hydrogen showed a strong
dependence on both the operating temperature and gas concentration
(Fig. 7). For the same operating temperature, the response of the

Fig. 3. SEM image of the SnO2–Au thin film. Fig. 5. UV–VIS absorption and reflectance spectra of a SnO2–Pt a) and, SnO2–Au b) film.
1112 I. Fasaki et al. / Thin Solid Films 518 (2009) 1109–1113

Fig. 6. Response of SnO2 (A), Pt–SnO2 (B) and Au–SnO2 (C) at 180 °C, (D) at 150 and (E) at 85 °C Au–SnO2 thin films.

localized either O− or O− 2 depending on the temperature. In the modified SnO2 film. The electron gain increases the film conductivity,
presence of metal (Pt or Au) catalysts on the sensor surface, the which is reflected in the drop in the initial sensor resistance. The
hydrogen gas splits up into hydrogen atoms, which form protons by generated protons get associated with the surface adsorbed oxygen-
donating the electrons to the conduction band of nanocrystalline ions (O− or O−
2 ions) and hop from one oxygen-ion to another. During
I. Fasaki et al. / Thin Solid Films 518 (2009) 1109–1113 1113

phase. The concentration increase of free charge carriers in SnO2


correlates with the partial pressure of molecules in the gas phase
[7,11,12].
The stability of the sensors was also investigated and was found
that they had a good response (approximately the same) even six
months after fabrication. We believe that especially the SnO2–Au
sensor might be a promising device for future applications.
As far as the recovery time is concerned, it depends on several
factors such as a) hydrogen removal flow, b) chamber's dead volume,
c) gas flow dynamics inside the test chamber, d) sticking coefficient of
the gas on the sensor surface, e) operating temperature, etc. [8]. In our
case the recovery time was several minutes.

4. Conclusions

Modifying SnO2 with Au nanoparticles decreased the sensor


working temperature with respect to the unmodified one from 180
down to 85 °C, while the response increased almost by 50 times.
Hydrogen detection as low as 500 ppm was then possible. These
results were less pronounced when SnO2 was modified with Pt
nanoparticles.

Acknowledgements

The authors would like to acknowledge the support of the Hellenic


General Secretariat for Research and Technology through a bilateral
Greek–Romanian cooperation program 2005–2007.

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