August 2002

Materials Letters 55 (2002) 327 – 333

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Formation and investigation of sol–gel TiO2 –V2O5 system

T. Ivanova a, A. Harizanova a,*, M. Surtchev b
a
Central Laboratory of Solar Energy and New Energy Sources, Bulgarian Academy of Sciences,
Blvd. ‘‘Tzarigaradsko chaussee’’ 72, 1784 Sofia, Bulgaria
b
Faculty of Physics, Sofia University, Blvd. ‘‘James Bouchier’’ 5, Sofia, Bulgaria

Received 15 March 2001; received in revised form 1 November 2001; accepted 5 November 2001

Abstract

A TiO2 – V2O5 colloidal solution was obtained with a stability of more than 2 years. Xerogels, dried at 80 BC and treated at
300 and 560 BC, were investigated by Fourier transform infrared spectroscopy (FTIR). Powder X-ray diffraction (XRD)
measurements showed that the sample treated at 300 BC is amorphous, and crystallization began after 450 BC. Vanadium-doped
titanium dioxide thin films were prepared by using sol – gel dipping technique. Highly transparent TiO2 – V2O5 coatings were
formed on quartz substrates. The optical properties of the sol – gel mixed thin films were characterized as a function of the
annealing temperatures from 200 to 650 BC. D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Sol – gel; Titanium dioxide; Vanadium oxide; Coatings

1. Introduction The mixed oxide system TiO2 – V2O5 could be ob-

The transition metal oxide films have found wide
applications as gas sensors [1], catalyst [2], and in op-
tical electronics [3]. Since titanium dioxide is one of
the most important materials in the industry, its pro-
perties have been extensively studied. Apart from this,
it has shown interesting photocatalytic [4] and electro-
chromic behavior [5].
On the other hand, vanadium pentoxide films have
received significant attention during the previous years,
and they are studied mostly due to their broad industrial
applications in optical switching devices [6], in humid-
ity sensors [7], secondary Li batteries, and also as elec-
rochromic electrodes [8].
tained by different deposition techniques. Specifically,
the sol – gel method offers a simple and cheap syn-
thetic route for the preparation of nanocrystalline thin
films. It should be noted here that titanium – vanadium
oxides also find applications as electrochromic mate-
rial [9] and lithium cells [10].
In this work, we report a sol – gel route for obtaining
mixed oxide system. The TiO2 – V2O5 powder samples
are characterized by XRD and FTIR analysis. The
coatings are obtained by a dipping method on quartz
substrates and are optically investigated by UV-VIS
spectrophotometry.
2. Experimental

*
Corresponding author. Fax: +359-2-754016. The TiO2 – V2O5 system is prepared by the sol – gel
E-mail address: tonyhari@phys.bas.bg (A. Harizanova). method. Fig. 1 shows the scheme of preparation of the

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X ( 0 2 ) 0 0 3 8 7 - 7
328 T. Ivanova et al. / Materials Letters 55 (2002) 327–333

Fig. 1. Scheme for the preparation of TiO2 – V2O5 sol.

colloidal dipping solution. The first step is the for-
mation of titanium dioxide sol: the precursor is tita-
nium ethoxide (Fluka, > 97%), introduction of 1.4 M
acetic acid causes an exothermic reaction, gelation is
obtained when 60 mol of water is added. One molar
acetylacetonate is used as peptizant. More details of
the formation of titanium dioxide sol are given in
Ref. [11]. The vanadium component involved as V2O5
powder is dissolved in hydrogen peroxide (30%). The
reaction is strong exothermic, and so H2O2 is added
dropwise with continuous stirring and cooling. The
two solutions are mixed and aged for 1 week at room
temperature, getting a red color. Experiments with
different Ti/V ratios were carried out. In this paper,
we investigate the solution with the highest stability
up to 2 years and with the formula 0.97TiO2 –
0.03V2O5.
The thermal transformation of xerogel and the for-
mation of crystalline oxide were observed with X-ray
powder diffraction. X-ray analysis was performed
 T. Ivanova et al. / Materials Letters 55 (2002) 327–333
with a URD6 diffractometer with secondary graphite
monochromator using Cu Ka radiation (35 kV, 20
mA) and applying the step method with 0.05B step and
constant counting times per step —15 s. Two different
configurations of the experiments have been ap-
plied —the standard Bragg –Brentano and the graz-
ing-incidence asymmetric X-ray diffraction (GIAX
RD).
The analyzed samples for the XRD observation
were dried at 80 BC in air and the obtained xerogels
were additionally treated at 300, 430, and 560 BC for 1 h
in air.
Gel powders were dried at 80 BC and a part of them
was thermally annealed at 300 and 560 BC for infrared
spectroscopy. Then, the samples were incorporated in
KBr pellets. The analysis was performed with Fourier
transform infrared spectrophotometer Perkin-Elmer
1600 in the regions 480 – 4000 cm 1.
Uniform coatings of TiO2 –V2O5 on quartz sub-
strates have been obtained by dipping in the colloidal
solution (the withdrawal speed around 10 cm min 1).
After drying at 80 BC for 2 h, the films had been put
under thermal treatment up to 560 BC in air with the
rate of 10 BC min 1 and after that, cooled down with
the rate of 20 –25 BC min 1.
We obtained pure TiO2 coatings by a similar sol –
gel method [11], and were used for comparison.
Fig. 2. FT-IR spectrum of TiO2 – V2O5 xerogel, treated at the temperature of 80 BC in air for 1 h.
329
The optical properties of the mixed oxide thin films
deposited on the quartz substrates were characterized
by UV –VIS Perkin-Elmer spectrophotometer in the
range of 250 –800 nm as a function of annealing tem-
perature.
3. Results and discussions
3.1. Infrared study of titanium –vanadium oxide sys-
tem
FTIR investigations were made for the TiO2 –V2O5
samples treated at three temperatures: dried at 80 BC
and annealed at 300 and 560 BC for 1 h in air. The
highest annealing temperature was chosen for com-
parison with similar investigation for the pure sol – gel
titanium dioxide.
Fig. 2 shows the spectrum of xerogel dried at 80 BC.
The band at 3851.3 cm 1 (not shown here) could be
assigned to octahedral vacancies and designated as
3+
6Ti –OH [12]. A characteristic band of the associated
hydroxyl group appeared around 3417 cm 1 (not
shown here). The 1762.7 cm 1 band is considered to
be the CMO monomer stretching vibrations [13]. The
set of the two bands at 1711 and 1280.8 cm 1 is attri-
buted to the m(COO) vibrations of an acetate ligand.
330 T. Ivanova et al. / Materials Letters 55 (2002) 327–333
The frequency separation value Dm = 430.2 cm 1 of
this doublet suggests an existence of a monodentate
acetate ligand [13,14]. The bands at 1660 –1630 cm 1
are owed to the vibrations of HCO3 group.
The absorption bands, which appeared in the
spectrum between 1000 and 1100 cm 1, are attributed
to the OR groups linked to Ti [13]. The characteristic
absorption peak of titanium ethoxide, which is the
precursor of the sols, appears at 933.3 cm 1 [15]. The
band around 818.9 cm 1 is suggested to belong to the
vibrations of polyhedral TiOn with coordination num-
ber less than 6 [14]. The absorption peak at 663.8
cm 1 may be described as the same as the vibration of
TiO6 octahedral with different kinds of ligands. The
weak band at 487.7 cm 1 is assigned to the influence
of the vanadium component.
Fig. 3 shows the FTIR spectrum of the TiO2 –V2O5
system at the annealing temperature of 300 BC in air.
The weak absorption band at 3793.1 cm 1 is probably
due to octahedral vacancies and designated as 6Ti3+ –
OH. The 3665.7 cm 1 band is characteristic for tetra-
hedral-coordinated vacancies and designated as 4Ti4 –
OH. The broad band centered at 3382.0 cm 1 is due
to the stretching vibration of the OUH bond. The
bands around 2974.8 cm 1 are attributed to the stretch-
ing vibration of the CUH bond of the organic com-
Fig. 3. FT-IR spectrum of TiO2 – V2O5 xerogel, treated at the temperature of 300 BC in air for 1 h.
pounds [16]. The group of peaks 1500– 1622 cm 1 is
attributed to the bending vibrations of water molecules.
The CH3 groups’ stretching vibration is found at
1403.1 cm 1 [13]. The band at 1088 cm 1 is assigned
to the bond TiUOUC. Another absorption band,
situated around 1048 cm 1, appeared only at the
spectrum for that temperature. Some authors [17] are
attributing this band as VMO bond of oxide-like
structure. At the higher annealing temperature, this
band has disappeared. The 880 cm 1 band is assigned
to the OUO stretching vibration in H2O2 as it is re-
ported that hydrogen peroxide is not released at the
temperature of 350 BC [18]. The absorption peak at 601
cm 1 is assigned to the VUO bond.
Fig. 4 shows the spectrum of sample treated at
560 BC for 1 h in air with comparison of pure tita-
nium dioxide sample treated at the same condition.
The water incorporation is found with two groups
of peaks: at around 3550 cm 1 (not shown here) and
around 1630 –1610 cm 1, characteristic of stretching
and bending vibrations of water molecules. The main
absorption peak of pure TiO2 (Fig. 4, curve 1) as-
signed to TiUO bond appeared at 511.9 cm 1. The
spectrum of the mixed system (Fig. 4, curve 2) shows
a number of bands at the low-frequency region. The
band at 604.3 and 590 cm 1 can be attributed to the
 T. Ivanova et al. / Materials Letters 55 (2002) 327–333 331

Fig. 4. FT-IR spectrum of TiO2 (curve 1) and TiO2 – V2O5 (curve 2)

xerogels, treated at the temperature of 560 BC in air for 1 h.

Fig. 5. XRD spectra of TiO2 – V2O5 xerogels treated at the tem-

VUO bond, appearing in the lower annealing tem- perature of 300 BC (curve 1), 430 BC (curve 2), and 560 BC (curve 3)
perature spectrum. The peaks at 493.9 and 468.4 cm 1 in air for 1 h.
are assigned to the TiUO bond.

3.2. X-ray powder diffraction

Fig. 5 presents XRD patterns of the xerogels trea-

ted at the temperatures of 300, 430, and 560 BC in air
for 1 h. The TiO2 –V2O5 powder annealed at 300 BC
shows no peaks and has a characteristic view of an
amorphous material. The sample treated at 430 and
560 BC is crystallized, showing an appearance of the
anatase phase titanium dioxide (according to JCPDS
card 21-1272) without any peaks attributed to the
vanadium oxide. Other authors also reported that
when the concentration of vanadium component is
smaller than 15%, there is no significant indication for
the presence of vanadium oxide [19]. Previous study
[11] on the formation and behavior of the sol – gel
titanium oxide system determined that the crystalliza- Fig. 6. UV – VIS spectra of sol – gel TiO2 – V2O5 thin films, treated at
tion began at 560 BC in the anatase phase of titanium the temperatures of 300 BC (curve 1), 400 BC (curve 2), and 500 BC
dioxide. In that case, the small amount of vanadium (curve 3) in air for 1 h, deposited on quartz substrates.
332 T. Ivanova et al. / Materials Letters 55 (2002) 327–333
Fig. 7. UV – VIS spectra of sol – gel TiO2 (curve 1) and TiO2 – V2O5
(curve 2) thin films, treated at the temperature of 560 BC in air for 1
h, deposited on quartz substrates.
additive decreases the crystallization temperature of
the anatase TiO2.
3.3. Optical properties of the TiO2 – V2O5 thin films
Uniform coatings were obtained by the dipping
method on quartz substrates and were optically char-
acterized by UV – VIS spectroscopy. The samples
were annealed at different temperatures from 200 to
650 BC. The sample treated at 560 BC in air for 1 h is
compared with pure TiO2 coating treated at the same
condition.
Spectral transmittance was measured in the 200 <
k < 800 nm wavelength range by use of a Perkin-Elmer
330 spectrophotometer. All the samples are very trans-
parent at the visible region. The measured samples are
with comparable thicknesses.
Fig. 6 displays transmittance spectra for the TiO2 –
V2O5 thin films annealed at three different temper-
atures: 300, 400 and 500 BC. It can be seen that the
transmittance in the visible range is high for the three
temperatures. At 300 BC, the percentage is near 80%,
above 400 nm for the amorphous phase of the system.
A different behavior is shown by the sample treated at
400 BC (Fig. 6, curve 2), where the curve is more ho-
rizontal and has some similarity with the curves for
annealing temperatures of 200 and 250 BC (not shown
here). The increase of the annealing temperatures from
500 to 650 BC with 50 BC step influences only a slight
decrease of the transmittance by 5 –10%.
Fig. 7 compares the transmittance spectra of the
pure sol – gel TiO2 and TiO2 – V2O5 thin films on
quartz substrates treated at 560 BC for 1 h in air. The
vanadium additive to titanium dioxide changes signifi-
cantly the transmittance in the 250– 500 nm region.
Both the curves in 500 – 800 nm looked relatively
plane and horizontal, with transmittance for pure
titania 5% higher.
The absorption was calculated from the transmit-
tance spectra (Fig. 7). The energy band gap values
were evaluated from the relation ahml(hm Eg)n for
indirect allowed transition (n = 2). From linear extrap-
olation towards the zero absorption of the plot of
(ahm)1/2 versus hm, we found Eg for the sol – gel-pre-
pared films.
The calculated values of Eg are: for the TiO2 –
V2O5 film, Eg = 3.32 eV and for TiO2, Eg = 3.67 eV.
The refractive index and thickness of titanium –
vanadium oxide coating on quartz substrate at the an-
nealing temperature of 560 BC were measured by LEF
3M ellipsometer at k = 638.2 nm. The values are
n = 2.27 and d = 77.5 nm.
4. Conclusion
The present work demonstrates the possibility of
preparation of sol –gel TiO2 – V2O5 system. The stabil-
ity of the obtained sol is more than 2 years, which
makes it useful and suitable for industrial applications.
The prepared thin films are highly transparent, uniform
with a one-layer thickness around 77 nm. Their optical
quality and very good adhesion towards different sub-
strates (ordinary glass and conductive glass) make these
thin films promising for wide range of applications.
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