Thin Solid Films 418 (2002) 7984

Elaboration and characterization of thin films of TiO2 prepared by sol

gel process
C. Legrand-Buscema*, C. Malibert, S. Bach
` Jarlan, 91025 Evry Cedex, France
LMN, Universite dEvry Val dEssonne, 1 rue du pere
Received 23 October 2001; received in revised form 27 June 2002; accepted 13 July 2002

Abstract
Solgel TiO2 thin films have been obtained by a dip-coating method on a silicon substrate. Very stable sols of this oxide were
synthesized using the alkoxide Ti(O-nBu)4 in the presence of acetic acid and using acetylacetone as a chelating agent. The film
thickness varied from 20 to 100 nm depending on the concentration of the sol for a monolayer thin film. The structural
characterization of this film on substrate Si(100) shows that the titanium oxide anatase phase is formed after heating at 400 8C
for 2 h. The appearance of the rutile phase depends on the substrate used. For example, the rutile phase appeared at 700 8C in
the xerogel while the presence of substrate Si(100) stabilizes the anatase phase up to 800 8C. The influence of the annealing
temperature on grain size has been evidenced. Indeed, the size of the particles found equal to 4 nm for films annealed at 400 8C,
increasing to around 40 nm at 800 8C.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Titanium oxide; Coatings; Solgel

1. Introduction
The development of TiO2 thin films is of particular
interest because of the numerous technological applications of this inorganic oxide. Using molecular precursors
to obtain an oxide network via inorganic polymerization
reactions, the solgel process provides new approaches
and a better control in the preparation of materials
compared with solid state reactions w14x. New morphologies can be obtained and new physical properties
may be expected depending on the structure which are
not produced by the usual processes w58x. This simple
method has also the advantage to produce particles in a
relatively shorter processing time at lower temperatures.
The rheological properties of sols and gels can give rise
to the formation of fibers and films and thus considerably increase the anisotropy of the material and its
chemical reactivity.
*Corresponding author. Fax: q33-1-6947-7665.
E-mail address: caroline.buscema@chimie.univevry.fr (C. Legrand-Buscema).

The film deposition can be performed by dip-coating.

This technique is a process where the substrate to be
coated is immersed in a liquid and then withdrawn at a
well-defined speed under controlled temperature and
atmospheric conditions.
This technique offers many advantages over other
deposition techniques due to the use of very simple
equipment. In addition, the stochiometry and the high
homogeneity of the final film can be controlled. Structural and micro-structural characterizations of thin films
have been realized by X-ray diffraction (XRD), atomic
force microscopy (AFM), scanning electron microscopy
(SEM).
The purpose of this paper is to investigate the preparation and characterization of solgel TiO2 thin films
dip coated on silicon. The solution parameters as acetylacetone (Acac)yTi, Acetic acidyTi ratios and concentration of the sol have been optimized in order to obtain
a stable TiO2 sol. The decomposition process of the sol
precursor was examined to determine the crystallization
temperatures and the phases obtained. The influence of
the concentration of the sol on the thickness, structure

0040-6090/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 0 2 . 0 0 7 1 4 - 9

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C. Legrand-Buscema et al. / Thin Solid Films 418 (2002) 7984

and micro-structure of the films were observed from

AFM and SEM experiments.
2. Experimental
Ti(O-nBu)4 is used as a raw material and n-BuOH as
a solvent. Jurek et al. w9x and Xu et al. w10x introduce
water in the solution to initiate hydrolysis. In our case,
using water induces the immediate formation of a white
precipitate due to the high reactivity of the alcoxide. As
it is of technical importance to obtain precursor solutions
with long-term stability, water is replaced by acetic acid
to decrease the kinetics of the hydrolysis and polycondensation of Ti(O-nBu)4. As titanium alkoxide is among
the most reactive, the speed of hydrolysis and condensation is very high, therefore, it is difficult to form a
stable sol. Acetylacetone (acac) is added as a chelating
agent to decrease the reactivity and stabilize the sol.
Then, acetic acid is slowly added to the alkoxide
solution with constant stirring. Acetic acid allows to
initiate hydrolysis via an esterification reaction as
follows:
ROHqR9COOHlH2OqRCOOR9
Moreover, it has been shown that acetic acid induces
the modification of the molecular structure of the precursor w11x. Here, steric hindrance is then reduced and
titanium (IV) reactivity is enhanced. A colorless sol
was obtained and at a concentration higher than 2.4 M,
it transformed into gel after 6 weeks. Since preparation
of thin films by dip-coating requires a weak concentration of sol (-0.5 M), another complexing agent must
be added.
The molar ratios of nacetic acid ynTi and nacac ynTi were
optimized to obtain stable sols of various concentrations
between 0.1 M and 0.5 M. The sols viscosities, measured
at 25 8C, are equal to 3.20 cSt for 0.1 M and 3.66 cSt
for 0.5 M.
In summary, the synthesis of various sols of TiO2 is
described in Fig. 1. TiO2 precursor solutions were
prepared first by stabilizing titanium n-butoxide, dissolved in n-butanol, with acetylacetone, stirring for 30
min. Acetic acid was then added to initialize hydrolysis
by esterification reaction with n-butanol. The final mixture was stirred for 30 min at room temperature. The
pH of the sols was less or equal to 2 and the sols were
stable for more than two months at various concentrations (0.1 M0.5 M). Xerogels were obtained after
calcination at 100 8C for 24 h.
Thermal Gravimetry Analysis (TGA) and Differential
Scanning Calorimetry (DSC) of the xerogel was done
using a Netzsch STA 409 analyzer. Samples were heated
from 25 8C to 800 8C at 10 8Cymin in a flowing air
environment. A Bruker D8 diffractometer using the
CuKa radiation was used to examine the XRD pattern
of powders and thin films. The diffractometer was
operated at 40 KV, 35 mA with a scanning speed of

Fig. 1. Flowsheet of the procedure preparing stable sol of titanium

(IV) by the solgel method.

0.028ymin at 2u-steps of 0.028. A digital Instrument

Nanoscope IIIa and a SEM Ziess DSM 982 Gemini
were used to examine the morphology of the thin films.
Thin films were fabricated by dip coating onto a precleaned silicon substrate (001). Indeed, cleaning of the
substrate is important for proper adhesion of the films.
It was cleaned ultrasonically in ethanol and air-dried at
100 8C.
Ten layers of solgel films were dipped onto the
substrate. Between each deposition, the film was calcined at 100 8C for 15 min. The structural and microstructural properties of the dipped films were studied
after annealing at 400, 500, 700 and 800 8C for 2 h
heating at 4 8Cymin in a flowing air environment. The
thickness of the samples, as measured by SEM, consisting of ten layers of 0.1 M sol concentration and 1 layer
of 0.5 M was equal to 200 and 100 nm, respectively.
In this paper, the structural and micro-structural properties of the films obtained at different temperatures will
be studied. The difference in structure and crystallization
temperature between xerogel and thin film will be
discussed.
3. Results and discussion
3.1. Characterization of xerogel
Fig. 2 shows TGA and DSC. The weight loss of the
xerogel finished at 300 8C. The weight loss occurred at

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81

Fig. 2. Simultaneous thermal analysis (TGAyDSC) of xerogel.

three temperature regions, namely, below 200 8C,

between 200 and 260 8C and from 260 to 300 8C. In
the first region (below 200 8C), the weight loss is
believed to result from the evaporation of water and the
thermal decomposition of the remnant organic solvents
such as butanol and water. Between 200 to 260 8C, the
weight loss is attributed to the carbonization or the
combustion of organic constituents in the sol precursor,
such as acetylacetone. Between 260 and 300 8C, the
weight loss is probably due to the evaporation of
physically absorbed water and the further combustion
of the remaining organic compounds.
After the weight loss, two exothermic peaks have
been observed at 480 and 560 8C. These two exothermic
peaks could be associated with two peaks of crystallization. It is assumed that these peaks can be ascribed to

the formation of the two allotropic forms of titanium

dioxide.
Fig. 3 shows a xerogel X-ray diffraction pattern of a
sample previously fired at 700 8C for 2 h. The peaks
were indexed with anatase, with a tetragonal symmetry
cs9.512 A),
and rutile, with a tetragonal
(as3.783 A,

cell (as4.593 A, cs2.977 A),

phases of dioxide
titanium. These two sets of parameters are very close to
those obtained for the classical TiO2 anatase w12x and
rutile phases w13x.
In relation with DSC (Fig. 2), the XRD pattern,
performed on xerogel previously baked at 700 8C,
evidenced the presence of two allotropic forms of TiO2:
anatase which crystallizes at 480 8C and rutile at 560
8C. Those results, i.e. the coexistence of two phases,
anatase and rutile at 700 8C in the xerogel, correspond

Fig. 3. XRD diffraction curve of xerogel experiment previously heated at 700 8C for 2 h (*: Anatase TiO2; qRutile TiO2).

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C. Legrand-Buscema et al. / Thin Solid Films 418 (2002) 7984

Fig. 4. XRD diffraction curves of thin films baked at several temperatures.

Fig. 5. SEM and AFM micrographs of the thin films baked at different temperatures for 2 h (a) 400, (b) 700, (c) 800 8C.

C. Legrand-Buscema et al. / Thin Solid Films 418 (2002) 7984

83

to those obtained by Suresh et al. w14x. The authors

have shown that pH modification extends the thermal
stability of the anatase phase by about 100 8C, compared
to an unmodified one. For pHF4, the thermal stability
of the anatase phase was also increased.
3.2. Characterization of thin films
The thin films deposited on a (001) Si single crystal
following the process described in experimental part
were analyzed by (u, 2u) diffraction. Fig. 4 shows thin
film X-ray diffraction patterns of a sample previously
annealed at several temperatures between 400 to 800 8C
for 2 h.
The samples crystallization appears at 400 8C and
XRD thin film patterns of samples baked between 400
to 700 8C show only the anatase phase. At 800 8C, the
rutile phase appears and coexists with the anatase phase.
Compared with xerogel, the crystallization of the rutile
phase is here delayed by the presence of the substrate
and so the silicium substrate stabilizes the anatase phase.
As we observe the main diffraction peaks of the
anatase phase, we can conclude that grains of thin films
were disoriented. The important full widths at half
maximum (FWHM) of diffraction peaks for annealing
at 400 8C decrease with increasing annealing temperature: growing grain is then induced.
For comparison, Fig. 5 shows the evolution in the
morphology of the thin films baked at different temperatures. It can be seen that the thin films baked between
400 to 700 8C have the same grain shape, but with
increasing annealing temperature the grain size increases. It can be seen too that inter grain porosity and
roughness appears and increases with increasing annealing temperature. The roughness measured by AFM
experiments increases from 2 nm to 7 nm with increasing
annealing temperature. At 800 8C, another grain shape,
elongated, flat, anisotropic, appears corresponding to
crystallization of the rutile phase. The roughness of thin
films was very high in comparison with that of the
substrate (equal to 0.2 nm). The quality of thin films
was excellent and crack free. These results were in
accordance with those of XRD.

Fig. 6. SEM micrographs of the thin films dipped for different concentrations of the sol and baked at 500 8C for 2 h (a) 0.1 M, 10
layers; (b) 0.5 M, 1 layer.

It has been evidenced that sol concentration influences

thickness and grain size. Indeed, grain size and thickness
increase with increasing sol concentration.
4. Conclusion
We have performed a TiO2 solgel synthesis using
alkoxide Ti(O-nBu)4, dissolved in n-butanol, in presence
of acetylacetone as a chelating agent and acetic acid.
The optimization of the molar ratio allowed a stability
control up to two months. Better results can be obtained
with nacac ynTis0.3, nacetic acid ynTis0.2.
With this experimental method of coating, the good
quality of the resulting thin films can be observed with
no crack. The study of thin film structure shows the
influence of substrate. Indeed, the thermal analysis
associated with XRD experiments show that the presence of substrate Si(100) stabilizes the meta-stable
anatase TiO2 phase and delays the appearance of the
rutile phase even at a high temperature (800 8C). In the
case of powder, the rutile phase appears at 560 8C. The
grain size and thickness increase with increasing sol
concentration.
Acknowledgments
The authors would like to thank Ecole Nationale

Superieure
des Mines de Paris (ENSMP) for SEM
experiments.
References

3.2.1. Influence of the concentration

We have studied the influence of the concentration of
the sol on the morphology of thin films. Two different
mono-layers were synthesized, the first one dipped with
a sol of concentration equal to 0.1 M, the second dipped
with concentration of sol equal to 0.5 M, both baked at
500 8C for 2 h. Cross section observations of the two
samples show that for 0.1 M concentration the thickness
is equal to 20 nm and for 0.5 M concentration the
thickness was equal to 100 nm (Fig. 6).

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