Thin Solid Films 515 (2006) 2678 – 2685

www.elsevier.com/locate/tsf

Transport and sensors properties of nanostructured

antimony-doped tin oxide films
T.R. Giraldi a , M.T. Escote a,⁎, A.P. Maciel b , E. Longo b , E.R. Leite a , J.A. Varela b
a
CMDMC/LIEC/Departamento de Química, UFSCar-Av. Washington Luiz, km 235, CP 676, CEP 13565-905, São Carlos, São Paulo, Brazil
b
CMDMC/LIEC/ Instituto de Química, UNESP-Araraquara, R. Prof. Francisco Degni, s/n, CEP 14801-907, Araraquara, São Paulo, Brazil
Received 17 May 2005; received in revised form 25 November 2005; accepted 22 June 2006
Available online 17 August 2006

Abstract

Tin oxide thin films doped with 7 mol% antimony oxide multilayer were prepared by the polymeric precursor method. Morphological
characterization revealed films with round-shaped grains, nanometric size (∼ 13 nm), and low roughness. These films display high transmittance
(∼ 80%) in the visible range of transmittance spectra, which is desirable for transparent conductive oxide films. Analysis on electrical resistivity
versus temperature data showed two different conduction mechanisms toward the temperature range. The gas sensor properties measurement of
the thicker thin film revealed good sensibility for the NOx.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Tin oxide; Polymeric precursor; Variable-range hopping; Gas sensors

1. Introduction
Transparent conductive oxides (TCOs) have been extensively
studied due to their important technological applications, such as
electrochromatic displays, solar cells, and other optoelectronic
devices [1]. For these applications, the TCOs should present a
combination of high transparency in the visible spectral range
and low electrical resistivity. An example of these oxides is the
tin oxide (SnO2) that shows high transmittance in the visible
region and a poor conductivity (σ ∼ 102–103 Ω− 1 cm− 1) at
room temperature (∼ 300 K). Moreover, σ value is unstable
during its operation due to the reaction of oxygen vacancies in
the SnO2 lattice with ambient oxygen [2]. Such properties can be
improved by doping the tin oxide with, for example, antimony
(Sb), indium (In) or fluorine (F). In fact, by increasing the doping
concentration (> 2%) a degenerate semiconductor is formed,
displaying higher σ values (> 103 Ω− 1 cm− 1). Since this doping
level is not too high, doped-SnO2 thin films are transparent for
visible light, which make them useful for a device application
⁎ Corresponding author.
E-mail address: mescote@liec.ufscar.br (M.T. Escote).
0040-6090/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2006.06.025
point of view. Then, the nature, quantity, and structural dis-
tribution of the doping are important factors for the electrical
properties of SnO2 [3].
In this context, several studies on the influence of the Sb5+
substitution in the tin oxide are reported and have shown that
high level doping (> 2%) promote a decrease of the resistivity
(ρ) values and keep the optical transparency in a wavelength
range that includes the visible region [4–8]. These works
revealed that Sb-doped tin oxides presents a low resistivity
(ρ ∼ 10− 3 Ω cm) and maintain 80% of its transparency at room
temperature. Therefore, this system has been extensively
studied for potential application in electro-optical systems.
Other interesting characteristic of TCOs is their gas sensors
properties [9] and among those oxides the SnO2 is often used as a
gas sensor mainly due to its high sensitivity to small concentrations
of gases [10]. The introduction of dopants produces additional
adsorption sites on the surface of SnO2 particles [11], impeding
particle growth [12] and resulting in a significant increase of the
specific surface area. For these reasons, Sb-doping has been used
on the SnO2 sensors in order to improve their conductivity and
sensibility of the sensor, which also is related to Sb content [13].
In general, several works reported on the synthesis and
characterization of SnO2:Sb films and a variety of methods have
 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
been used to grow antimony-doped tin oxide thin films as, for
example, sputtering [4], spray-pyrolysis [5], electron-beam [6],
sol-gel [7], and dip coating of chemical solutions [8]. Among
these methods, the polymeric precursor method stands out and
presents several advantages over other methods, such as its low
cost and the excellent quality (high homogeneity and low
roughness) to produce SnO2:Sb films [8,14].
A pioneer study of Bernardi et al. [8,14] examined the in-
fluence of the dopant concentration and the solution's viscosity in
the deposition of thin films by this chemical route on the struc-
tural, electrical, and optical properties of Sb-doped SnO2 thin
films. Also, a previous work showed that the polymeric pre-
cursors route provide high quality nanostructured Sb-doped tin
oxide thin films [15]. However, we believed that some parameters
deserve more detailed investigation as, for example, the transport,
sensor, and optical properties.
In this context, this work describes the synthesis and charac-
terization of 7 mol% Sb-doped tin oxide (SnO2:Sb) multilayer
thin films. They were deposited on amorphous silica substrates
by the polymeric precursor technique. Characterizations were
performed on these films to verify the influence of morpholog-
ical properties in the transport and sensors properties of these
films. In fact, this chemical procedure allowed the production of
nanostructured samples that displayed interesting sensor
properties and allowed the study of mechanisms involved in
the low temperature (< 300 K) transport measurements.
2. Experimental details
The SnO2 thin films with 7 mol% of Sb2O5 were prepared by
the polymeric precursor method and deposited onto amorphous
silica substrates, details are described elsewhere [14,15]. The
precursor solution was deposited by the spin-coating technique
and dried on a hot plate (∼ 150 °C), followed by a two-stage
heat treatment. In the initial stage, the films were calcined at
temperature of 300 °C for 2 h to promote the pyrolysis of the
organic material. In the second stage, the films were heat-treated
at 650 °C for 2 h. To produce a multilayer film, several layers
were deposited on the substrates, and each one was submitted to
a thermal treatment prior to the next deposition. Through this
procedure, we have prepared films with 1, 4, 6, and 7 layers and
thickness varying from 150 to 988 nm.
Scanning tunneling microscopy (STM) studies of these films
were carried out using a Digital Instruments-Nanoscope III-A
system, operating under ambient conditions. The imaging was
performed using a Pt-Ir nanotip, in the constant current mode with
zero input filters and by using a moderate feedback gain, as provide
in the software. The images were obtained with bias voltage
smaller than 100 mV, at tunneling currents close to 100 pA. This
STM images were taken to obtain topographic images of the films
and morphological information (grain size, shape, and surface
roughness). The cross section and the thickness of these films was
analyzed by field emission scanning electron microscopy (FE-
SEM), which was performed in a Jeol 7400-F microscopy using an
acceleration voltage of 3 kV and working distance of 3 mm.
The optical transmittance and reflectance measurements
were carried out ex situ (in air) using an ultraviolet-visible-near
2679
infrared (UV-Vis-NIR) Cary 5G spectrophotometer from 2000
to 200 nm. The scan rate was 600 nm/min and bandwidth of the
light source in the UV-Vis-NIR region was 1 nm. The spectrum
of the substrate was taken as baseline and the baseline cor-
rection procedure was executed prior to each measurement
session. The refraction index and thickness were evaluated by
ellipsometry. This characterization was taken in a Jobin Yvon
ellipsometer, with a He-Ne laser beam (λ = 632.8 nm) and an
incidence angle of 70° to the normal angle of the sample.
Characterization by electrical resistivity ρ(T) as a function of
temperature was performed to examine the conduction mecha-
nisms of the SnO2:Sb thin film. The temperature dependence of
ρ(T) was measured with a commercial Physical Properties
Measurements System PPMS model 600 from Quantum De-
sign. These measurements were taken during both cooling and
heating processes and in the 10–300 K temperature range. Four
copper leads were attached with Ag epoxy. The ρ(T) data were
evaluated by the van der Pauw technique, considering a pre-
determined film thickness.
The measurements of the sensor properties were carried out in
a chamber with a fixed volume of 1.4 L (Gefram 500 equipment)
with controlled temperature and pressure. A Pirani Balzers
(model TPR250) sensor controlled the pressure, while Cole
Parme solenoid valves adjusted the gas flow. The resistance
measurements were performed in a 34401A Hewlett Packard
digital multimeter.
The experiments were conducted in the following stages:
(a) initially the chamber was evacuated; (b) the samples were
exposed to alternate cycles of air (20% O2 and 80% N2) and air/
NOx mixture flows. Each cycle consisted of a flow of air (White
Martins) of 669 mL/min for 10 min, followed by a flow of air
(669 mL/min) mixed with NOx of 4 mL/min for 5 min. Resistance
values were measured during these cycles. After 10 min of
airflow, Rair was measured and, after the 5 min exposure to NOx,
Rg was determined. The sensitivity of the sensor (S) was assessed
by the following equation:
Rair −Rg
S¼j j100
Rair
The results of the sensitivities for a given temperature were
obtained in triplicate.
3. Results and discussion
3.1. Morphological characterization
The morphological characteristics of the SnO2:Sb thin film
deposited on amorphous silica substrates were analyzed by
STM. An example is shown in Fig. 1 that displays the surface
morphology for the thicker film with thickness of ∼ 988 nm. All
samples present a smooth and crack-free surface and the mor-
phological parameters (shape and grain size, roughness) were
analyzed by means of the Nanoscope IIIA software. Through the
root mean square average of height deviations, taken from these
images, this software evaluate the surface roughness (RMS),
which for the films studied here presents values relatively low,
2680 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
Fig. 1. STM images of the 988 nm thick SnO2:Sb film.
indeed the RMS values range from 0.40 to 0.65 nm. These RMS
values are lower than those of 2–16 nm reported in literature for
Sb-doped SnO2 thin films grown by plasma-enhanced chemical
vapor deposition, sputtering, sol-gel techniques on glass
substrates [16,17]. However, the RMS measured in thin films
is comparable with that of 0.6–1.3 nm reported for a SnO2:Sb
films prepared by the polymeric precursor method [8]. These
analyses also revealed the presence of round-shaped grains with
an average grain size of 13 nm, which is rather smaller than those
observed of 30–70 nm by Kim et al. [16] for similar films. Such
results suggest that the preparation technique strongly affects the
surface roughness and the grains size.
Fig. 2. Secondary electron FE-SEM cross-section images of (a) single-layer thin film (150 nm) and (b) multilayer thin film (988 nm); (c) BSE image of the multilayer
thin film (988 nm).
An additional characterization of the morphological properties
of these films was made by the cross-section field-emission
scanning electron microscopy FE-SEM. Fig. 2 shows the cross-
section morphology by FE-SEM of the films composed of one
layer (∼150 nm) and seven layers (∼988 nm). The pictures
revealed homogeneous mesoporous films with grain size ranging
from 9 to 15 nm, which are in good agreement with the STM
results. No significant difference in the film morphology (grain
size and porosity) was observed between the single layer and the
multilayer samples, as indicated in the secondary electron image
of Fig. 2(a) and (b). Through the FE-SEM analysis, it is also
possible to observe a well-defined interface between the several
layers of the multilayer sample, as illustrated in the backscattering
electron (BSE) image of Fig. 2(c). In fact, Goebbert et al. observed
similar behavior for the multilayer morphology of SnO2:Sb and
SnO2:In thin films processed by chemical solution deposition
method [17].
These set of results suggested that SnO2:Sb films prepared
by the polymeric precursor method presents a microstructure
features with slight difference from those reported in literature
[16,17]. The single-phase samples displayed nanosized grains,
which are rather smaller than those reported in literature [16,4].
In addition, some authors discussed the effect of grain size on
sensor and optical properties of undoped-SnO2, they observed a
clear dependence of sensitivity [18,19] and the optical constants
[20] with the size of the SnO2 particles. Therefore, to verify the
influence of microstructure on the physical properties of SnO2:
 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
Fig. 3. Transmittance spectra of Sb-doped SnO2 films deposited on amorphous
silica substrates with various thicknesses: (a) 150 nm, (b) 388 nm, (c) 600 nm,
and (d) 988 nm.
Sb samples were characterized by means of optical, transport,
and sensors properties.
3.2. Optical characterization
Fig. 3 shows the transmittance obtained in the near infrared
NIR and UV–Vis region spectra for all SnO2:Sb films. The
transmittance spectra measured in the visible range in air consist
of a broad maximum absorption close to wavelength
λ ∼ 424 nm for all samples. At high λ values (> 1000 nm), the
decrease of the transmission is in general attributed to the high
reflection of the free electrons. It can also be observed that the
transmission varied from 70% to 90% for all the thicknesses
studied. The clear decrease of the transmittance throughout the
spectral range is more evident for the thicker sample
(t ∼ 988 nm). In general, the decreasing of NIR transmittance,
also called plasma region, can be related to the increase of the
thickness of these films from 150 to 988 nm. In films with
different Sb5+ content, such behavior is explained on the basis
of the changes in transport properties of these films. Also, it has
been observed that the electrical resistivity decreases as SnO2:
Sb films became thicker [21], this decrease of the resistivity
Fig. 4. Full line: Transmittance spectrum of the thicker SnO2:Sb film. Dashed
line: theoretical spectrum obtained through the Drude theory.
2681
with the thickness can be responsible for the reduction in the
transmission of these films. As all films present the same Sb
content, it is believed that this variation can be attributed mainly
to the difference in the thickness. In fact, the thickness together
with the porosity of the samples can be the main factor for the
higher optical scattering and, consequently, to the absorption
losses in the NIR and infrared region.
In this context, we have simulated the transmittance spectra of
these films using the Drude theory [21]. These simulations were
performed considering the plasma frequency ωN ∼ 5.7 × 1015 s− 1,
which were calculated by the density of electrons N ∼3 × 1027 m− 3
and effective mass m⁎ = 0.27 m0, and damping frequency
Γ ∼ 5.88 × 1014 s− 1, which were reported by Nutz et al. [21].
Through these data we have estimated the transmittance spectra for
these films, and it was possible to verify that the IR region seems to
be fitted by the Drude theory. Fig. 4 displays an example of
experimental and calculated spectrum for the thicker film. It is
observed in this figure that not all the spectrum can be very well
fitted by this model, and one possible explanation is that the N value
used for this simulation is one order of magnitude larger than those
obtained previously by Hall effect measurements [15]. However,
these simulations of the transmittance spectra in the IR region,
which can be related to the intraband absorption of free electron and
position of the plasma Edge, seems to agree with this electron
density.
To study the sharp ultraviolet absorption edge of SnO2:Sb
films with different thickness, the optical absorption coefficient
(α) has been deduced from optical transmittance spectra and
reflectance spectra (not shown) of SnO2:Sb films in the 200–400
wavelength range. These α values are derived from the relation
α = (1/t)log[(1 − R)2/T] [22], where T is the transmittance value,
Fig. 5. (i) Absorption coefficients derived from transmittance data as a function
of energy and (ii) (αhν)2 versus hν for the for the Sb-doped SnO2 films deposited
on amorphous silica substrates with various thicknesses: (a) 150 nm, (b) 388 nm,
(c) 600 nm, and (d) 988 nm.
2682 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
R is the reflectance value and t is the film thickness. Fig. 5(i)
presents α as a function of the energy (hν) for the thinner and
thicker films. This figure revealed a small variation in the
absorption band behavior as a function of the film thickness.
Such result, as discussed previously, is also expected, because it
is believed that all samples present almost the same amount of
carrier density as suggested by the previous discussion.
To estimate the optical band gap (ΔE), the absorption co-
efficient has been analyzed in terms of the relation [23]:
hma~ðhm−DEÞ; ð1Þ
here α is the absorbance, hν is the energy. Extrapolating the line
to photonic energy (hν), the ΔE value is obtained (see Fig. 5
(ii)). A small variation of these values as a function of the film
thickness was found since these ΔE values are close to 3.8–
3.9 eV. From these results, it is believed that ΔE seems to be
independent of the film thickness. These ΔE values are also
close to those of 3.1–4.1 eV reported in literature [7,24–27].
This difference can be related to defects derived from the
chemical procedure used to prepare the samples as discussed by
Terrier et al. [7]. In fact, some works reported that the presence
of nanoporous on silicon films could promote the presence of
quantum confinement, which leads to an increase in the band-
gap energy [28]. As we have produced mesoporous SnO2:Sb
films, this variations on the ΔE values can be related to the
presence of such quantum confinement effect. Meanwhile, the
absence of shift in the absorption coefficient bands and the
small change in the ΔE values suggested that Burnstein-Moss
(BM) effect and the porosity shift seem to have a small
contribution to the optical absorption band [29]. In fact, such
effects occur in films with different amount of carrier and in
nanostructured porosity. As all samples display similar carrier
density and porosity, the BM and the porosity effects seem to
have no significant contribution to the optical properties of these
films. It is believed that the thickness promotes the main
changes in the absorption coefficient of these SnO2:Sb films.
The refraction index of SnO2:Sb thin films have been evaluated
from ellipsometry measurements. These measurements revealed
refractive indexes of n ∼ 1.40–1.45 for films with thickness
Fig. 6. Temperature dependence of the electrical resistivity of Sb-doped SnO2:
Sb thin films with different thicknesses: (a) 388 nm, (b) 600 nm, and (c) 988 nm.
ranging from 150 to 988 nm, respectively. These n values agree
with n ∼ 1–2 observed for antimony-doped tin oxide film with
different antimony content [30]. These low n values can also be
related to the absence of interference fridges in transmittance
spectra of the SnO2:Sb films, but Santhi et al. [5] obtained clear
interference fridges in the transmission spectra of similar films and
with n values close to those reported in this work. Then, it is
believed that it could be also related to the microstructure of these
mesoporous samples with nanometric grain sizes.
Also, with these data, we have estimated the packing density
for the films through the following equation [7]:
n2b −n2 1−n2
f þ ð1−f Þ ¼ 0: ð2Þ
n2b þ 2n2 1 þ 2n2
Here f is the packing density, nb is the SnO2 bulk refraction
index (nb ∼ 1.997), and n is the film refraction index. We have
obtained f values ranging from 0.43 to 0.48, which seem to be in
agreement with the FE-SEM analysis discussed earlier. Such
results also suggest that the porosity of a multilayer film is
similar to that of a single layer film. In fact, by estimating the
porosity and grains areas using the FE-SEM images (see Fig. 2),
it is possible to make a rough estimative of the porosity in the
cross section of these films. These analyses revealed that all
samples present porosity close to 65%. This values means that
65% of the films are porous and 45% are the particles and grains
based on the cross section analyzed of the film. As the packing
density f is the volume fraction of particles in the films, we
believed that such result agree with the f values found by the
ellipsometry measurements.
3.3. Electrical characterization
To examine the temperature dependence of electrical re-
sistivity ρ(T), we took ρ(T) measurements of SnO2:Sb thin
films with different thicknesses, as shown in Fig. 6. These data
revealed that, in every sample, there was a clear increase in the
ρ(T) values as the temperature decreased. These curves possibly
indicate a semiconductor-like behavior. In fact, the same be-
havior was also observed in ρ(T) curves for similar thin films
reported in the literature [31,32].
A comparison of ρ(T) data obtained for samples with diferent
thicknesses showed a clear increase of the magnitude of ρ(T) as
the thickness decreased. The ρ(300 K) values drop from ∼16 to
6.5 mΩ cm as the thickness increased from 388 to 988 nm. This
thickness dependence of ρ(T) values of these films was likely
related to the contribution of charge carrier scattering from the
film surface. An increase in such scattering with decreasing film
thickness has generally been reported [33]. In this work, we
found ρ(300 K) values in good agreement with those of
ρ(300 K) ∼ 10− 3 Ω cm reported in the literature for SnO2:Sb
thin films [32]. Another factor that could contribute to change in
electrical resistivity values as a function of film thickness is their
porosity. However, the morphology images and optical measure-
ments revealed that the single and multilayer films have almost
the same porosity. Then the decrease of ρ(T) with the SnO2:Sb
films thickness is not related to the porosity.
 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
At room temperature (∼ 300 K), the conduction mechanism
in these SnO2:Sb (0.6–16%) thin films is attributed to ionized
scattering. Conversely, below this temperature, some research-
ers have proposed an activated conduction mechanism for ρ(T)
curves of SnO2 doped with 1–16% of Sb [7,30]. It is important
to notice that the authors were able to adjust the ρ(T) data to this
model because they used a temperature range of 80–400 K for
these measurements [30,32]. In fact, in this temperature range,
the log(ρ(T)) versus 1/T curves seem to display a linear
behavior, suggesting an Arrhenius conduction mechanism for
these samples (see the inset of Fig. 6).
To study this feature of the transport properties of the SnO2:
Sb samples, these resistivity data were fitted to a generalized
form of the activated hopping model, in which the electrical
resistivity is given by [7]:
qðT Þ ¼ q0 expðTm =T Þ1=m ; ð3Þ
where ρ0 is the residual electrical resistivity, Tm is a constant,
and m = 1 and 4 correspond, respectively, to the Arrhenius and
variable range hopping mechanisms.
We found that, above T ∼ 100 K, these curves displayed a
simple activated mechanism; therefore, all the curves were fitted
using m = 1. This behavior is shown in Fig. 7, which displays
the linear fitting obtained for log(ρ(T)) versus 1/T curves of the
SnO2:Sb films, which considered Tm = Ea/kB. As described in
the literature, in this mechanism, Ea is the activation energy and
kB is the Boltzmann constant. Ea is usually described as the
energy needed to promote the charge carrier across the Coulomb
potential between an occupied and an unoccupied site. By
means of these fittings, we obtained energy values ranging from
Ea ∼ 1.1–2.5 meV, which are in good agreement with the
Ea ∼ 0.7 and 1.3 meV obtained for SnO2 thin films with 4% and
16% of Sb reported by Santhi et al. [27].
Below T ∼ 100 K, as is shown in Fig. 8, the best fit for the ρ(T)
data was achieved using m = 4 for both samples with thicknesses
of ∼600 and 988 nm. It was observed that the log(ρ(T)) versus 1/T
values (m = 1) display a nonlinear behavior in this range of
temperature. Based on these fittings with m = 4, the calculated Tm
temperature parameter varied from 0.95 to 1.22 K. This feature
suggests that the conduction mechanism for T < 100 K can be
interpreted as a variable-range hopping, VRH, mechanism. In this
Fig. 7. log(ρ(T)) versus 1/T curves for the SnO2:Sb thin film samples with
various thicknesses: (a) 200 nm, (b) 600 nm, and (c) 988 nm.
2683
Fig. 8. log(ρ(T)) as a function of T−1/4 for the SnO2:Sb (7%) thin films with
different thicknesses: (a) 388 nm, (b) 600 nm, and (c) 988 nm.
case, the Tm of expression (3) is called characteristic temperature,
and relates to the density of states N(ε) at the Fermi level and to
the localization length α− 1, as follows:
Tm ¼ ba3 =kB N ðeÞ; ð4Þ
where β is related to the space dimension for hop. The VRH
mechanism normally occurs at low temperatures (T < 300 K), in
which the energy is insufficient to excite the carrier across the
Coulomb gap. Hence, the conduction takes place by hopping of
small region (∼kBT) in the vicinity of Fermi energy, and it is also
assumed that N(ε) remains almost constant. To examine the VRH
conduction, the constant β was assumed to be 16 for a three-
dimensional hopping [34], and α− 1 ≈ 3.19 Å, which is related
with the distance between neighboring Sb atoms estimated from
the structure refinement for SnO2:Sb (6.2 at.%) compounds
reported by Ambegaokar et al. [35]. With these values, the density
of states was calculated as N(ε) ≈ 4–5 × 1019 eV− 1 cm− 3.
These values of N(ε) can also be used to estimate the Fermi
energy of the SnO2:Sb films. The following relation was used to
calculate EF [36]:
N ðeÞ ¼ ð3=2ÞN =EF ; ð5Þ
where N is the charge carrier density, which was assumed to be
N ∼ 10 21 cm − 3 as a result of Hall effect measurements
performed on similar samples in a previous work [15]. Using
these values, The calculated EF were 0.07 and 0.09 eV for the
samples with thickness of 388 and 988 nm, respectively. These
values are rather lower than those of EF ∼ 0.7–0.8 eV obtained
for SnO2 thin films doped with fluorine reported in literature,
with different carrier concentration values [36]. By means of
these results, it is believed that this point deserves a more
detailed study, but it will not be the focus of this work.
3.4. Sensor properties
To verify the sensitivity of the 988 nm thick thin films to the
NOx gas, we have performed a NOx gas sensor testing in these
samples. Fig. 9 illustrates the variations in the thin film sensitivity
as a function of the temperature. In fact, this figure revealed a
maximum sensitivity in the temperature range of 200 and 400 °C.
2684 T.R. Giraldi et al. / Thin Solid Films 515 (2006) 2678–2685
Fig. 9. NOx sensitivity (S) of the 988 nm thick Sb-doped SnO2 thin film.
In the second and third measurements, it was observed a clear
reduction in the material's maximum NOx sensitivity. It is
believed that it occurs due to the strong interaction between the
adsorbed NOx and the surface of the oxide. Therefore, one of the
greatest existing problems in this type of sensor seems to be the
reproducibility of signal intensity. Moreover, after heat treatment
at 500 °C for two hours in an O2 flow, the film recovered the
sensitivity value similar to the initial one.
Such a results are in good agreement with those observed for
sintered pellets of pure tin oxide nanoparticles and reported by
Maciel et al. [12]. In their study, a maximum NOx sensitivity was
obtained at 400 °C, which is ∼100 °C higher than the value found
for the Sb-doped SnO2 thin film. Two main factors might have
contributed to this decrease in the maximum sensitivity tem-
perature: (a) the nanostructured thin film form and (b) the anti-
mony doping. The presence of antimony allows highly conductive,
nanostructured, and mesoporous thin film to be obtained.
3.5. General discussion
An analysis of structural, electrical, optical, and sensor pro-
perties of the SnO2:Sb thin films indicated its excellent quality
suitable for application as multitask thin film devices (TCOs
and sensors). The structural properties are directly correlated to
the good quality of thin films. The fact that the films are
nanostructured is responsible for the absence of significant
transmittance variations as their thickness increases. Moreover,
being mesoporous, the films possess good sensor properties,
rendering this material suitable for the detection of NOx. The
processed thin film displayed low resistivity, a behavior that has
been extensively reported in the literature [4–8]. However, this
paper discusses an as yet unpublished study of the electronic
conduction mechanism in the SnO2–Sb system.
From this study, the ρ(T) data appear to display two distinct
conduction mechanisms: (a) at T > 150 K, the ρ(T) curve could
be fitted as a thermally driven activation mechanism; and (b) at
T < 150 K, the data were found to obey a variable-range hopping
law. This behavior is usually observed in several families of
semiconductors and, in general, is presumably associated with a
Coulomb disorder. It can be assumed that the replacement of Sn
from the SnO2 lattice by Sb is the possible source of the VRH
behavior. Therefore, this conduction mechanism can be
attributed to the substitution of Sn for Sb in the SnO2 lattice.
4. Conclusions
The polymeric precursor method was effective for obtaining
Sb-doped SnO2 thin films with high transparency, low roughness
and resistivity, characteristics, which are very important in
electro-optic applications. A decrease in resistivity occurred as
the thin film thickness increased. The smallest value observed was
6.5 × 10− 3 Ω cm, corresponding to a 988 nm thick thin film.
The NOx sensitivity of the 988 nm thick thin films was studied
in a temperature range of 200–400 °C, with maximum sensitivity
occurring at 300 °C. The values of the maximum sensitivity
temperature showed good reproducibility, although the signal
intensity decreased as the number of measurements increased.
However, this sensor material can be regenerated by heat treatment.
Thus, Sb-doped SnO2 thin films obtained by the polymeric
precursor method are examples of multitask devices. The polymeric
precursor method is excellent for producing highly homogeneous
doped materials and thin films with nanostructure characteristics.
Acknowledgements
The authors would like to thanks to Prof. V. Bouquet for the
ellipsometry measurements and to Prof. A.J. Chiquito for the
discussion concerning the electrical properties. Also, the
authors acknowledge the financial support from the Brazilian
funding agencies FAPESP (Fundação de Apoio a Pesquisa do
Estado de São Paulo) and CNPq (Conselho Nacional de
Desenvolvimento Científico e Tecnológico).
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