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Characterization and hydrogen gas sensing properties of TiO2 thin films

prepared by sol–gel method

Article in Applied Surface Science · October 2012

DOI: 10.1016/j.apsusc.2012.07.030

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Applied Surface Science 259 (2012) 270–275

Contents lists available at SciVerse ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Characterization and hydrogen gas sensing properties of TiO2 thin films prepared
by sol–gel method
Azhar Ali Haidry a , Jarmila Puskelova b , Tomas Plecenik a , Pavol Durina a , Jan Gregus a , Martin Truchly a ,
Tomas Roch a , Miroslav Zahoran a , Melinda Vargova b , Peter Kus a , Andrej Plecenik a , Gustav Plesch b,∗
a
Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University, Bratislava, Slovakia
b
Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia

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

Article history: Thin films of titanium dioxide with thickness of about 150 nm were deposited by spin coating method
Received 13 December 2011 on a sapphire substrate from a sol–gel and annealed at various temperatures (from 600 ◦ C to 1000 ◦ C).
Received in revised form 29 June 2012 Structural, optical and hydrogen gas sensing properties of the films were investigated. The annealing
Accepted 6 July 2012
temperatures from 600 to 800 ◦ C led to anatase phase with grain size in the range of 14–28 nm. Further
Available online 14 July 2012
increase of the annealing temperature resulted in transformation to rutile phase with larger grain size
of about 100–120 nm. The optical band gap tended to decrease with increasing annealing temperature.
Keywords:
The estimated values of activation energy for charge transport were in the range of 0.6–1.0 eV for films
TiO2
Sol–gel
annealed at temperatures from 600 ◦ C to 800 ◦ C and 0.37–0.38 eV for films annealed at 900 ◦ C and 1000 ◦ C.
Annealing effect The films annealed at 900 ◦ C and 1000 ◦ C showed better hydrogen sensitivity, what can be at least partially
Grain size caused by their higher surface roughness.
Surface roughness © 2012 Elsevier B.V. All rights reserved.
Band gap
Activation energy
Hydrogen gas sensor

1. Introduction
There is, nowadays, a great demand for hydrogen gas sensors,
since hydrogen is emerging as an important source of energy.
Among others, metal oxide (MOX) sensors based on SnO2 , ZnO,
WO3 , TiO2 and other oxides have attracted much attention in the
field of gas sensing due to their low cost and flexibility in pro-
duction, simplicity of their use, high stability and large range of
detectable gases [1–4]. Despite of many advantages, selectivity and
high operating temperature are the main issues which need to be
improved [5,6]. The selectivity can be generally improved either by
doping of the MOX by various metals [7,8] or by using sensor arrays
[9,10].
The sensing mechanism of MOX is based on surface reactions
with gases in the atmosphere which produce changes in their con-
ductivity. Oxygen from the atmosphere can be adsorbed on the
surface of the MOX in the form of different species (O2 − , O2− and
O− ) depending on the operating temperature [1], e.g.:
O2(gas) + 2e− ↔ 2O− (ads)
∗ Corresponding author. Tel.: +421 2 60296 273; fax: +421 2 60296 273.
E-mail address: plesch@fns.uniba.sk (G. Plesch).
The adsorbed oxygen decreases (in the case of n-type semicon-
ductor) the conductivity of the MOX film by trapping electrons
from the surface and forming a depleted surface layer. The oxygen
can be desorbed by introducing a reducing gas, such as hydrogen,
according to the following equation:
H2(gas) + O− (ads) → H2 O(des) + e− (2)
In this reaction the trapped electrons are returned back to the
conduction band and the conductivity of the film is partly or fully
restored (Fig. 1). Concentration of reducing and oxidizing gases can
thus be detected by monitoring the MOX conductivity [1–4].
Although recently the sensing layers are frequently replaced by
nanotubes [11] and nanostructured materials [12], the develop-
ment of new and improved thin film sensors is still important since
they can be prepared by cheap and simple methods. Among other
techniques, the wet chemical sol–gel procedure based on hydroly-
sis and polycondensation of metal alkoxides is well suited for the
preparation of high-purity nanocrystalline metal oxide thin films
(1)
[13,14]. It has several advantages over other procedures (e.g. mag-
netron sputtering), which includes low-cost of the precursors and
the apparatus, uncomplicated and rapid deposition and an ability of
easy control and modification of the layer composition. Therefore
it is frequently used for preparation of MOX sensors [15,16].

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.07.030
 Author's personal copy
A.A. Haidry et al. / Applied Surface Science 259 (2012) 270–275
Fig. 1. The surface reaction mechanism at the surface of TiO2 thin film (the
interaction of H2(gas) with adsorbed oxygen forming H2 O(gas) molecules) and the
measurement scheme of the resistance response of the thin films.
In the previous work the annealing effect on the optical, struc-
tural as well as on hydrogen gas sensing properties of TiO2 thin
films prepared by magnetron sputtering has been studied [17,18]
and it has been shown that the annealing temperature has great
influence on the gas sensing properties of the films. In this work
we present such studies of the annealing effect on properties of
TiO2 films prepared by sol–gel technique.
2. Experimental
Selection of suitable substrate plays important role in charac-
terizing thin films. Despite the fact that silicon based wafers are
cheap and well suited for MEMS applications, the sapphire sub-
strates provide the following practical advantages [19–21]: they
are transparent and well suited for optical and XRD characteri-
zation, possess very high resistivity (1015  cm) and thus do not
affect the sensing signal of the active layer, they have good thermal
conductivity and exhibit good thermal and chemical stability, what
makes them suitable for applications in harsh and high temperature
environment.
In our case, single crystal c-cut (0 0 0 1) sapphire wafer sub-
strates with a dimension of 10 mm × 10 mm were used. Initially
the substrates were washed using ultrasonic bath in sequence for
15 min in acetone, isopropanol and deionized water and subse-
quently dried for 5 min at 90 ◦ C. The TiO2 thin films were synthe-
sized by spin-coating from a sol–gel, which was prepared according
to procedure described in [22,23]. A mixture of 3.8 ml of ethanol
with 0.7 g of Triton X-100 was mixed under ambient conditions for
3 min. Then 0.68 ml of acetic acid and 0.36 ml of Ti(IV) isopropoxide
were added. The spin-coating procedure was repeated three times
using a velocity of 3000 rpm with short intermediate heating at
550 ◦ C.
After deposition, the TiO2 thin films were annealed in air
at various temperatures ranging from 600 ◦ C to 1000 ◦ C for 1 h
with a ramping of 100 ◦ C/15 min in MTI GSL-1600X-S60 tube
furnace. Subsequently a Pt thin film of 20 nm thickness was
deposited by dc magnetron sputtering. Standard photolithogra-
phy and subsequent Ar ion beam etching was then used to pattern
comb-like Pt micro-structures with 10 ␮m distance between the
electrodes.
271
The structural investigation of the TiO2 thin films was performed
by ex situ measurements of grazing incidence x-ray diffraction
(GIXRD) on a X’Pert Pro MRD thin film diffractometer (PANalyt-
ical) using Cu K␣ radiation (45 kV, 40 mA). We have used fixed
low incidence angle of 0.6◦ with incidence beam parabolic mir-
ror producing low divergence (0.05◦ ) parallel primary beam. The
incidence angle was optimized at the first diffraction position
for maximum intensity. The detector was scanning diffraction
angle range 20–70◦ in 2 using a parallel plate collimator (diver-
gence of 0.18◦ ). For the step size of 0.05◦ the counting time was
30 s.
Thickness of the films was determined in cross-section by Scan-
ning Electron Microscope (SEM) TESCAN TS 5136 MM. Surface
topography of the films was analyzed by Atomic Force Micro-
scope (AFM) NT-MDT Solver P47 PRO in semi-contact mode using
standard Si tips. The transmission optical spectra in the range of
300–700 nm were obtained by SPECORD UV VIS spectrometer (Carl
Zeiss Jena).
A computer-controlled experimental setup was used for the
gas-response measurements. All measurements were done in a
sealed chamber (volume of 300 cm3 ) in flow regime of the syn-
thetic dry air at the rate 0.1 l/min. Amount of gas flowing to
the chamber was controlled by two gas flow controllers, Red-y
Smart Mass Flow Meter and Controller by Icenta Controls Ltd.,
one for synthetic air and one for synthetic air with 1% of H2 with
ranges of 15–500 sccm and 3–100 sccm (standard cubic centime-
ters per minute), respectively. The sample was mounted on a
Boraelectric heating element from Advanced Ceramics Corp. with
a K-type thermocouple inside. DC power supplied to the heater
was regulated by PID algorithm to maintain the desired tem-
perature on the thermocouple. The electrical resistivity of the
TiO2 thin films was measured by a Keithley 6487 Picoamme-
ter/Voltage Source. This setup allows us to measure resistance R
up to ∼1011  at various H2 concentrations ranging from 300 ppm
to 10 000 ppm and various operating temperatures up to 350 ◦ C.
The resistance vs. temperature (RT) measurements were performed
in temperature range from 250 to 350 ◦ C, while the gas sens-
ing measurements were done at temperatures from 100 ◦ C to
350 ◦ C.
Fig. 2. XRD patterns of the TiO2 thin films annealed at temperatures ranging from
600 ◦ C to 1000 ◦ C, where A is anatase, R is rutile and Pt and Ag peaks are from
platinum electrodes and silver paste respectively.
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272 A.A. Haidry et al. / Applied Surface Science 259 (2012) 270–275

Table 1
Properties of the TiO2 films: surface roughness and an average grain size obtained from the AFM, size of nanocrystals determined from the XRD spectra, optical band gap Eg
obtained from optical transmittance spectra and activation energy EA calculated from the R–T curves.

Sample (◦ C) Surface roughness (nm) Average grain size (nm) Band gap, Eg (eV) Activation energy EA (eV)

AFM XRD

600 0.57 18 14 ± 2 3.47 1.07

700 0.55 15 28 ± 6 3.43 0.88
800 1.89 21 15 ± 2 3.41 0.65
900 11.74 96 130 ± 40 3.01 0.37
1000 13.48 120 100 ± 30 2.80 0.38

3. Results and discussions 3.2. Surface topography and film thickness

3.1. Structural characterization
The XRD patterns of the films annealed in the range of
600–1000 ◦ C are shown in Fig. 2. Weak and broad diffractions of
the anatase TiO2 phase can be observed for thin films annealed
in temperature range of 600–800 ◦ C. The grain size was calculated
according to Debye–Scherrer equation [24] from the full width
at half maximum (FWHM) of the anatase (1 0 1) diffraction to
be in the range of 15–28 nm (Table 1). It is in accordance with
Refs. [22,23], where nanocrystalline TiO2 films with high surface
area have been prepared in presence of Triton X-100 surfactant
and controlled water amount for hydrolysis of Ti alkoxide, which
was formed in situ by esterification reaction of organic acid and
alcohol. The presence of a non-ionic surfactant plays a crucial
role in organizing the structure of the material and in creating
well defined and reproducible nanophases. The films annealed at
900 and 1000 ◦ C consisted of pure rutile phase with grain size
of 100–130 nm calculated from FWHM of its (1 1 0) diffraction
(Table 1).
Thickness of the as deposited thin films was estimated in cross-
section by SEM to be about 150 nm (Fig. 3a). The surface topography
and roughness were analyzed by AFM (Fig. 3, Table 1). The aver-
age surface roughness SA was calculated as standard deviation of
N 2
height h adopting the formula: SA = i=1
(hi − h̄) /N where hi is
height of the ith point, h̄ is average height and N is number of
points. Thin films annealed at 600–800 ◦ C exhibit nano-crystalline
surface with grain size up to 21 nm and average roughness in the
range of 0.6–1.9 nm (Fig. 3b–d and Table 1). On the other hand the
films annealed at 900–1000 ◦ C showed the presence of larger grains
with average size of 100–120 nm and roughness in the range of
11.7–13.5 nm (Fig. 3e and f and Table 1).
3.3. Optical characterization
Transmittance spectra have been used to determine the opti-
cal energy gap (Eg ) of the films (Fig. 4). The dependence of (˛E)2
vs. E, where ˛ is the absorption coefficient and E is the photon

Fig. 3. SEM micrograph of the cross section of the as deposited film (a), AFM topography of the TiO2 thin films annealed at 600 ◦ C (b), 700 ◦ C (c), 800 ◦ C (d), 900 ◦ C (e) and
1000 ◦ C (f).
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A.A. Haidry et al. / Applied Surface Science 259 (2012) 270–275 273

Fig. 4. Transmittance spectra of the TiO2 thin films and the energy band-gap. Left: Optical transmittance spectra of the TiO2 thin films annealed at various temperatures.
Right: The typical plot for (˛E)2 vs. photon energy E for the thin film annealed at 900 ◦ C, which shows how the Eg values were determined. The inset shows a plot of the energy
band gap vs. post-deposition annealing temperature.

energy, was extrapolated by linear curve (Tauc’s plot). The values
of Eg (Table 1) were evaluated from the intersection of the linear
part of the above extrapolation, assuming ˛2 = 0 (Fig. 4) [25,26].
The band-gap energies of TiO2 thin films (anatase, Eg = 3.2 eV; rutile,
Eg = 3.0 eV [27]) predetermine that TiO2 absorbs the radiation in the
UV region. The films annealed at temperatures 600–800 ◦ C exhibit
Eg values in the range of 3.4–3.5 eV (Table 1). It is in accordance
with Ref. [28], where it has been shown that in nanocrystalline TiO2
thin films the decrease of particle size below ∼30–40 nm shifts the
energy gap to higher values due to the quantum confinement. For
the films annealed at 900 and 1000 ◦ C the Eg values are 3.01 and
2.80 eV and they correspond to values which are typically found for
rutile [27]. We propose that the distinctly decreased transmission
observed in the visible region above 400 nm for samples annealed
at 900 and 1000 ◦ C originates mainly from scattering losses caused
by higher roughness of the rutile films as reported by [25].
3.4. Arrhenius plots
Measurements of the electrical resistance of the prepared struc-
tures as a function of the operating temperature (from 250 ◦ C to
350 ◦ C) were performed in synthetic air at a rate of 0.2 ◦ C/s. The
activation energy for charge transport (EA ) for each film in the
above temperature range was determined by plotting Arrhenius
plots (Fig. 5) from the resistance vs. temperature (R–T) charac-
teristics, satisfying the following equation: Rair = R0 exp(EA /kB T),
where kB is the Boltzmann constant and T is the absolute temper-
ature. The obtained values of the activation energy EA , which can
be considered as the energy required for transport of the charge
carriers [29,30], are shown in Table 1. Gradual decrease of the EA
was observed with increasing annealing temperature up to 900 ◦ C.
This is in agreement with results reported by Deshmukh et al. [31],
where inverse proportionality of EA with increasing annealing tem-
perature was also observed.
Since the films prepared in this research showed n-type conduc-
tivity, the value of R corresponded to decrease of the electrical
resistance from Rair to Rgas when H2 is introduced into the cham-
ber. This decrease of the electrical resistance is given by reduction of
the depleted surface layer and increase of number of charge carriers
caused by the chemical reaction (2).
Various dynamic responses of the thin films were recorded for
each sample. Fig. 6 left shows the dynamic response of the sens-
ing layer with highest sensitivity (annealed at 900 ◦ C) recorded at
300 ◦ C. This sensing layer exhibited high sensitivity for low con-
centrations of H2 gas but as the concentration was increased above
3000 ppm it showed abnormal behavior. Above this concentra-
tion the resistance first decreased and then after a time interval
it started to slightly increase. Similar behavior was also observed
when this sensing layer was exposed directly to higher concentra-
tions (10,000 ppm) of the gas (Fig. 6 right). This effect was observed
more dominantly at lower temperatures.
The estimated values of the response times ( res ) and recovery
times ( rec ) for 300 ppm and 10,000 ppm H2 concentrations, esti-
mated as time required to reach 90% of the resistance change, are
shown in Table 2. In general, relatively fast response and recovery
times were observed for all films.
The operating temperature at which the sensitivity of the
thin film is maximal (Top,max ) along with corresponding maximal

3.5. Hydrogen gas sensing properties

Sensitivity (S) of the thin films to the hydrogen gas was calcu-
lated as the ratio of the change in the electrical resistance caused
by the introduced gas (R = Rair − Rgas ) to the electrical resistance
of the thin film in the gas, Rgas [1,17,18].

Rair − Rgas R Rair Fig. 5. Arrhenius plots – linear fit of ln(Rair ) vs. the reciprocal temperature con-
S= = ∼ (4) structed from R–T measurements of the TiO2 thin films recorded in the temperature
Rgas Rgas Rgas range from 250 ◦ C to 350 ◦ C.
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274 A.A. Haidry et al. / Applied Surface Science 259 (2012) 270–275

Table 2
The values for Top,max , maximum sensitivity of the films and response and recovery times for 300 ppm and 10,000 ppm H2 gas.

Sample (◦ C) Top,max (◦ C) S at Top,max S = Rair /Rgas  res (90%) – for 300 ppm (s)  res (90%) – for 10,000 ppm (s) ␶rec (90%) – for 10,000 ppm (s)

600 ∼210 2.9 × 102 ∼190–220 ∼90–100 ∼550–600

700 ≤225 1.3 × 101 ∼200–220 ∼40–50 ∼490–520
800 ∼300 1.0 × 101 ∼130–150 ∼45–55 ∼330–360
900 ≤220 5.6 × 104 ∼220–240 ∼90–110 ∼400–440
1000 ∼225 8.1 × 103 ∼240–250 ∼120–130 ∼420–450

Fig. 6. Typical dynamic response of the thin films annealed at 900 ◦ C. Left: Dynamic changes in the electrical resistance upon the introduction of increasing concentrations
of H2 gas ranging from 300 ppm to 10,000 ppm for a cycle of 10 min (measured at operating temperature Top = 300 ◦ C). Right: Typical dynamic response of the thin film to
10,000 ppm of H2 gas measured at different operating temperatures. The measurement was done with a cycle of 15 min for gas in and gas out at each temperature in the
range from 100 ◦ C to 250 ◦ C.

Fig. 7. The annealing effect on sensing properties of TiO2 thin films prepared by sol–gel method. Left: Sensitivity to 10,000 ppm of H2 concentration vs. operating temperature.
Right: The effect of annealing temperature on the properties (sensitivity, surface roughness and activation energy) of TiO2 thin films.

sensitivities are shown in Table 2 and Fig. 7 left. The highest sensi-
tivity was obtained for films annealed at 900 ◦ C followed by the
films annealed at 1000 ◦ C, both consisting of rutile phase with
large (∼ 100 nm) grains and high surface roughness. The value of
EA for both films is relatively small (0.37 eV and 0.38 eV respec-
tively) and Top,max is about 220–225 ◦ C. The films annealed at
temperatures from 600 ◦ C to 800 ◦ C, which consisted of anatase
phase with smaller (∼18–21 nm) grains and exhibited higher values
of EA (0.6–1.07 eV), showed considerably lower sensitivity which
was decreasing with increasing annealing temperature. One of the
factors behind the improved sensitivity of the films annealed at
900 and 1000 ◦ C can be the increased surface roughness, as the
increased surface area offers more adsorption sites. A correla-
tion between surface roughness, surface area and sensitivity was
reported in [32] for NiO films. Relationship between the sensitivity,
surface roughnes and activation energy for our samples is shown
in Fig. 7 right.
4. Conclusions
Structural, optical and gas sensing properties of TiO2 thin films
deposited on sapphire substrate by spin coating of sol–gel and
annealed in temperature range of 600–1000 ◦ C were studied. The
films annealed at 600–800 ◦ C consisted of anatase phase with
small grains (15–28 nm) and low surface roughness, exhibited
higher activation energy for charge transport EA (0.65–1.07 eV).
The complete transformation to rutile phase was observed in
the films annealed at 900–1000 ◦ C which contained large grains
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A.A. Haidry et al. / Applied Surface Science 259 (2012) 270–275
(100–130 nm) and exhibited high surface roughness and smaller
values of EA (0.37–0.38 eV). The optical results confirmed decrease
of the energy band gap Eg (from 3.47 eV for nanocrystals of anatase
to 2.80 eV for larger grains of rutile) with increasing annealing
temperature. The films annealed at 600, 700 and 800 ◦ C showed
relatively low sensitivity to hydrogen gas (2.9 × 102 , 1.3 × 101 and
1.0 × 101 respectively for 10,000 ppm of H2 ), while sensitivity of
the films annealed at 900 and 1000 ◦ C was considerably higher
(S = 5 × 104 and 8 × 103 respectively). We propose that the increase
of sensitivity of these films can be at least partially related to
increased surface roughness offering more adsorption sites.
Acknowledgements
This work was supported by the Slovak Research and Devel-
opment Agency (APVV) under Contract No. LPP-0176-09 and
APVV-0199-10, by the Ministry of Education of the Slovak Repub-
lic under Contract VEGA 1/0605/12, by Comenius University Grant
UK/96/2012 and is also the result of the project implementa-
tion Grant Nos. 26220220004 and 26240220002 supported by the
Research & Development Operational Programme funded by the
ERDF.
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