18 Thin Solid kThns, 219 (1992) 18 23

Effects of solvent on properties of sol-gel-derived TiO 2 coating films

Lili Hu*, Toshinobu Yokot, Hiromitsu Kozuka and Sumio Sakka

Institute Jbr Chemical Research, Kyoto University, Uji. Kyoto-Fu 611 (Japan)
(Received November 26. 1991; revised February 21, 1992; accepted May 5, 1992)

Abstract

The effects of the kind of solvent on the properties of TiO2 coating films prepared by the sol-gel method using
titanium isopropoxide (Ti(OC3H7i)4) as the starting material have been investigated. Ethanol, ethanol mixed with
isopropyl alcohol, and ethanol with 2-ethoxyethanol were used as the solvents. The kind of solvent was found to
affect the crystallization behaviour, microstructure, and photoelectrochemical properties of the resultant TiO2
coating films.

I. Introduction 2. Experimental details

The sol-gel method is one of the most important
techniques for the synthesis of various functional coat-
ing films [1] because it possesses a number of advan-
tages over conventional film formation techniques, such
as low temperature processing, easy coating of large
surfaces, and possible formation of porous films and
homogeneous multicomponent oxide films. The present
authors [2] have applied the sol-gel dip coating method
for preparing semiconducting oxide films, such as TiO2,
SrTiO3, BaTiO3, c~-Fe20 3, which can be used as pho-
toelectrodes for the decomposition of water. As a
result, it was found that in the sol-gel-derived TiO2
films [3 6] the cell performance as a photoanode is
significantly affected by the pore characteristics, specific
surface area, and surface state of the film. It is pre-
sumed that such properties may be strongly dependent
on the sol gel processing conditions including the
kind and concentration of the solvent and the heat
treatment.
In the present study, the present authors focus on
the effect of the kind of solvent on the hydrolysis and
condensation reactions of Ti(OC3HTi)4, the crystalliza-
tion behaviour of the gel films, and the microstructure
and photoelectrochemical properties of the resultant
TiO 2 coating films. Three kinds of solvents, ethanol,
ethanol mixed with isopropyl alcohol and ethanol with
2-ethoxyethanol, were examined.
*On leave from Shanghai Institute of Optics and Fine Mechanics,
Academia Sinica, Box 8216, Shanghai, China.
"['Author to whom correspondenceshould be addressed.
2.1. Preparation o f Ti02 coating films
Three kinds of sols, TI, T2 and T3, for dip coat-
ing were prepared using ethanol, ethanol mixed with
isopropyl alcohol and ethanol mixed with 2-ethoxy-
ethanol respectively. They were prepared by mix-
ing titanium isopropoxide (Ti(OC3Hyi)4), anhydrous
ethanol (CzHsOH), isopropyl alcohol (C3H7OH), or
2-ethoxyethanol (C2HsOCH2CHzOH), hydrochloric
acid and distilled water in a similar way to that de-
scribed previously [3, 4]. The chemical compositions are
shown in Table 1. All chemicals were supplied by Wako
Pure Chemical Industries Ltd., Osaka. The equivalent
oxide content of TiO2 in these sols was kept constant at
10.8% by weight. Silica glass plates coated with Sb203-
doped SnO 2 conducting film (Nesa silica glass) were
used as substrates. The substrate was dipped in the sol
and withdrawn at a speed of 0.25 mm s - ~ to make a gel
coating film. The TiO2 gel films were heated to temper-
atures ranging from 300 °C to 900 '~C for 10 min in air.
The samples were put directly into a furnace which was
maintained at a given temperature.
2.2. Characterization
The crystallization behaviour of the TiO2 gel films
was examined by X-ray diffraction using Cu K~ radia-
tion. The as-prepared surface and the fracture surface
of the gel and ceramic coating films heated to 100 °C
and 500 °C respectively were observed by a Hitachi
model 450S scanning electron microscope. The thick-
ness and refractive index of the coating films were
measured by an ellipsometer (model DVA-36VW, Mi-
zojiri Optical Works, Tokyo) using an He Ne laser as
the light source.

0040-6090/92/$5.00 ,C 1992 ElsevierSequoia. All rights reserved

 L. Hu et al. / S o l - g e l TiO 2 coatings 19

TABLE I. Compositions and viscosities of starting solutions

Sol Composition (mol) TiO2 a Viscosity

(wt.%) q (cP)
Ti(OC 3Hi7 )4 C 2 HsOH C 3H 7OH C 2H50C2H4OH HCI H20

Tl 0.05 0.46 0.007 0.05 10.8 3.3

T2 0.05 0.265 0.15 -- 0.007 0.05 10.8 5.4
T3 0.05 0.41 -- 0.025 0.007 0.05 10.8 3.8

~Equivalent oxide content of TiO 2 in sols.

The photocurrent-potential curves for the TiO2
coating film used as a photoelectrode were measured
in a buffer solution of pH7 (0.2MNazB407+
0.14 M H2SO 4 + 0.3 M Na2SO4) using a potentiostat
(model HG-501, Hokuto Denki Co. Ltd., Tokyo). A
500 W xenon lamp (Ushio Denki Co. Ltd., Tokyo) was
used for illuminating the film electrode.
films prepared by dipping ten times in T1, T2 and T3 sols
respectively and heating at 500 °C for 10 min after each
coating. As seen in Figs. 2(c) and 2(d), both gel and
crystallized coating films from T2 sol consist of particles.
On the contrary, as seen in Figs. 2(a) and 2(e), a

3. Results

3.1. Thickness and microstructure of the Ti02 coating

films
Figure 1 shows the relationship between the film
thickness and the number of dippings for the TiOz
coating films which were obtained by heating the gel
films at 500 °C for 10 min after each dipping. A linear (a) (b)
relationship going through the origin was found to hold
for every sol. The average thickness of a fired film with lpm
one dipping was calculated to be 0.081 I~m, 0.115 lam
and 0.085 tam for T1, T2 and T3 sols respectively,
indicating that the film for one dipping is thicker for T2
sol than for T1 and T3 sols.
Figure 2 shows the scanning electron microscopy
(SEM) photographs of the films. Figures 2(a), 2(c) and
2(e) are the as-prepared surfaces of the films prepared
by dipping eight times in T1, T2 and T3 respectively
and heated at 100 °C for 10 min after each coating, and (c) (d)
Figs. 2(b), 2(d) and 2(f) are the fracture surfaces of the

u I i i i
1.2 roT1 ./
LO
0.8
o T3 //j

I (e) (f)
0 2 4 6 8 10 12
Number of dipping, Fig. 2. SEM photographs of the TiO 2 coating films from (a), (b) TI,
(c), (d) T2, and (e), (f) T3 sols. (a), (c), (e) As-prepared surfaces:
Fig. 1. Relation between the thickness and the number of dippings eight dippings; heated at 100 °C for 10 min after each coating. (b),
for the TiO 2 coating films. The coating films were heated at 500 °C (d), (f) Fracture surfaces: ten dippings; healed at 500 °C for 10 min
for 10 min after each coating. after each coating.
20 L. Hu et al. / Sol-gel TiO2 coatings

300'C, lOmin 400'C, lOmin

T1

T2
T3 ~ T3
I I I I I I [ I

20 30 40 5O 60 20 30 40 5O 60
(a) 20/deg (c) 2e/deg

350'C,
lOmin I j~ 450"C,
lOmin
TI
II
f T2

T3
I | I I

2O 30 40 5O 60 20 30 40 50 60
(b) 2e/deg (d) 2O/deg

900'C,10rain
0 0 anatllse

rutile
0

(a) T1

O
~ (b) T2

500"C,
10rain

is= %
1~1 ~ I (c) T3
_.~ .1~ T2

20 30 40 50 60 20 30 40 50 60
(e) 20/deg (f) 20/deg
Fig. 3. X-ray diffraction patterns of the TiO2 coating films obtained by heating the gel films at various temperatures.

layer structure is observed for the gel films from T1 and and 2(f) shows that the films from T2 sol have a rather
T3 sols heated at 100 °C, which then changes into a rough surface after heating at 500 °C, while those from
columnar structure on heating at 500 °C as seen from T1 and T3 sols have a smooth surface. In particular,
Figs. 2(b) and 2(f). A comparison of Figs. 2(b), 2(d) the film from T3 has a very smooth surface.
 L. Hu et al. / Sol-gel 7702 coatings 21

i , i ,
TABLE 2. Refractive index of TiO2 coating films prepared from
different coating solutions

Sample Refractive index for the following heating

T1
temperature (°C)

500

2.169
600

2.222
700

2.254
800

2.400
,., 0 I

500
i

600 700
I L

800
t
T2 2.078 2.111 2.207 2.353
T3 2.140 2.194 2.220 2.367
Fig. 4. Porosity of the TiO 2 coating films as a function of the
temperature of heat treatment.

3.2. Crystallization
Figure 3 shows the X-ray diffraction patterns of the
films. They were prepared by dipping 5 times in T1, T2
and T3 sols and heating at 300, 350, 400, 450, 500 and
900 °C for 10 rain after each coating. All the films are
amorphous at 300 °C, and anatase crystals are precipi-
tated at 350 °C, 400 °C and 450 °C for the films made
from T3, T2 and T1 sols respectively. Rutile phase is
found in T1 and T3 samples on heating at 900 °C, while
no trace of rutile phase is observed for the T2 sample at
900 °C.
3.3. Refractive index and porosity
Table 2 summarizes the refractive indices of the
coating films prepared by heating the gel films at 500,
600, 700 and 800 °C for 10 min. The crystalline phase
precipitated in these films was anatase. It is seen that
the refractive index increased with increasing heating
temperature in each of the T1, T2 and T3 series. It is
noticed that at a given temperature the refractive index
is larger in the order T2 < T 3 <T1. The values are
smaller than that of dense anatase, 2.52, found in the
literature [7].
The porosity of the coating films was calculated using
the equation [8]
n2--1
porosity :- 1
nd 2 - 1
where nd is the refractive index of pore-free anatase
(2.52 [7]), and n is the refractive index of the porous
coating film. The porosity-heating temperature curves
are shown in Fig. 4. The porosity decreased from
30%-40% for a heating temperature of 500 °C to 10%-
20% for 800 °C.
3.4. Photoelectrochemical properties
TiO2 coating films subjected to heat treatment at
500 °C for 10 min after each coating were employed
as photoanodes for photocurrent measurements. The
photocurrent-potential curves measured in an elec-
trolyte of pH 7 are shown in Fig. 5. The T3 sample had
the largest photocurrent of about 48 mA cm-2, while
the T1 sample had the smallest photocurrent of about
50
T8
i 40
30
20
T1
a , , ~dark
-1.0 -0.5 0.5 1.0 1.5 2.0
E / V vL 8CS
Fig. 5. Photocurrent-potential curves of the TiO 2 coating films ob-
tained from five dippings by heating at 500 °C for 10 rain after each
coating,
14 mA cm -z, indicating a big difference in cell perfor-
mance between the TiO2 film electrodes prepared from
different sols.
4. Discussion
4.1. Hydrolysis and condensation reactions
Titanium alkoxides have different structures depend-
(1) ing on the kinds of alkoxyl groups and/or solvents
[9, 10]. The titanium atom is tetrahedrally coordinated
in Ti(OC3Hvi)4, while it is pentahedrally coordinated in
Ti (OC2H5)4 [11, 12]. In addition, Ti(OC3H7i)4 in iso-
propyl alcohol is monomeric, while Ti(OC2Hs)4 in
ethanol is associated and solvated to form a dimeric
complex, Tiz(OC2Hs)8 • 2CzHsOH. Higher rates of hy-
drolysis and condensation reactions are expected for
monomeric alkoxides than for oligomeric alkoxides be-
cause there is less steric hindrance. This is revealed in a
previous study [13], where monodispersed, fine particles
are obtained by hydrolysing Ti(OCzHs) 4 in ethanol,
while non-monodispersed, large particles are formed
from Ti(OC3Hvi)4 dissolved in isopropyl alcohol.
In T1 sol of the present work Ti(OC3HTi)4 is dis-
solved in ethanol. So, it is possible that the ester
exchange between the isopropoxide and ethanol would
22 L. Hu et al. / Sol gel TiO: coatings
lead to the formation of a complex such as
Ti2(OC2Hs)8 x(OC3H7i),-2C2HsOH, which may
have a more oligomeric nature than monomeric
Ti(OC3HTi)4. On the contrary, in T2 sol, a larger
portion of Ti(OC3H7i)4 molecules would remain as
monomer than in T1 sol because of the addition of
isopropyl alcohol to the solvent. Then, the alkoxides in
T2 sol possibly have higher reaction rates of hydrolysis
and condensation than in T1 sol. This may be reflected
in the higher viscosity of T2 sol than T1 sol as shown in
Table 1. The higher reaction rates in T2 sol result in the
formation of larger particles in the sol and a rough
surface of the coating films, whereas the lower reaction
rates in T1 sol give rise to the formation of columnar
particles in the sol and a smooth surface of the film.
The hydrolysis and condensation in T3 sol are as-
sumed to proceed in almost the same manner as in T I
sol, since only a small amount of 2-ethoxyethanol was
added. In fact, similar values of viscosity and film
thickness, non-particulate, columnar structure of the
film and smooth surface were observed in both the TI
and the T3 samples.
4.2. Parameters affecting the film thickness
Orgaz and Capel [ 14] found that the film thickness t
of oxide glass coating films obtained by the dip coating
method obeys the following semiempirical equation:
t = (P~/Po) WKaO1V/psg),/2
where p~ and P0 are the densities of the sol and the
heat-treated glass film respectively, and W is the ratio
between heat-treated coating weight and liquid coating
weight, r/ is the viscosity of the sol, a is the surface
tension of the sol, K is a constant, V is the withdrawing
speed and g is the gravitational acceleration. Table 3
summarizes the viscosity r/and the surface tension a of
sols, the film thickness t per coating, and the ratio of
the film thickness t(Ti) of sample T2 and T3 to t(T1)
of sample T1, and the square root of the ratio of the
viscosity q(Ti) of T2 and T3 sols to q(T1) of T1 sol.
Since the equivalent TiO2 content of each sol and the
withdrawing speed are kept constant and the surface
tensions of the solvents are almost the same (see Table
3) in the present samples, the viscosity of the sol would
T A B L E 3. Parameters determining the thickness of sol gel-derived TiO2 coating films
Sample q (cp) ° a (dyn c m - t)b
TI 3.3 22.4
T2 5.4 22.0
T3 3.8 22.7
~'Measured viscosity of the sols.
bSurface tension of the solvent.
~Average film thickness per coating.
be the only parameter that governs the film thickness of"
TiO2 coating films. The values in the fifth column in
Table 3 are in good agreement with those in the last
column, indicating that the film thickness is controlled
mainly by the viscosity of the sols.
4.3. Crystallization behaviour
In TiO2 gel films prepared from T2 and T3 sols,
anatase phase precipitated at lower temperatures,
around 350-C and 400"C respectively, while those
prepared from T1 sol exhibited the highest crystalliza-
tion temperature (about 450 '~C). This indicates that the
addition of isopropyl alcohol or 2-ethoxyethanol to
ethanol promotes the crystallization of the TiO2 gel
films. A similar phenomenon was also reported by
Takahashi and Matsuoka [15], who found that the use
of diethanolamine instead of ethanol as a solvent for
Ti(OC3H7i)4 promotes the precipitation of both ana-
tase (about 400 °C) and rutile (about 650 cC) phases
out of TiO2 coating films.
Such a difference may be caused by (1) stress gener-
ated in the films and (2) different structures of particles
contained in the gel films. Since there are no significant
differences in particle structure between TI and T3
samples as seen from Fig. 2, the second cause cannot
explain the difference in crystallization behaviour. In
the present study, silica glass plates with Nesa coating
were used as the substrates, whose thermal expansion
(2)
coefficient is as small as 5 x 10 7 °C t. The TiO 2 gel
films tend to shrink as heat treatment proceeds, result-
ing in pore disappearance and densification. This, in
turn, produces tensile stress in the films, the magnitude
of which should increase as the densification proceeds,
in the order T2 < T3 < T1 in the present case, as ex-
pected from Table 2. Therefore, it may be concluded
that the crystallization into anatase phase is suppressed
by the tensile stress arising in the TiO2 films during
heating because it would accompany additional shrink-
age in the films.
4.4. Photoelectrochemical properties
Addition of isopropyl alcohol or 2-ethoxyethanol to
the starting coating solutions enhanced the photocur-
rent of the as-prepared TiO2 coating films as shown in
t (p.m) ~ t(Ti)/t(T1 ) [r/(Ti)/q(T1 )] ~/2
0.081 1 1
0.115 1.41 1.28
0.085 1.05 1.15
 L. Hu et al. / Sol-gel Ti02 coatings
Fig. 5. The possible reasons for the different photoelec-
trochemical properties are differences in (1) crystallinity,
(2) specific surface area, (3) electrical resistance of the
sol-gel-derived TiO 2 film electrodes, and (4) Ti 3 + con-
centration at the surface [4-6].
It is reasonable to assume that the crystallinity of the
TiO 2 coating films heated at the same temperature is
higher in the order T1 < T2 < T3, on the basis of the
observed crystallization temperature in the order
T3 < T2 < T1. The specific surface area increases in the
order T1 < T3 < T2 as expected from the porosity data
in Fig. 4 and the capacitance data obtained by the
impedance analysis, The capacitances measured at 0 V
(with respect to a saturated calomel electrode) in a
solution o f p H 7 were 0.14 F m - 2 for T1, 0.24 F m -2 for
T2, and 0.21 F m - 2 for T3, which obviously indicates
that the specific surface area increases in the order
T1 < T3 < T2 in accordance with the porosity data. In
addition, it was also found from the impedance analysis
of the TiO2 film electrodes that the TiO2 film resistance
in the dark is 470 f~ for T1,340 f~ for T2 and 180 f~ for
T3 samples, decreasing in the order of T1, T2 and T3
samples. These facts suggest that higher crystallinity,
lower resistance and larger specific surface area result in
the higher photocurrent of T2 and T3 films than of T1
film. A detailed discussion about the effect of solvents on
the photocurrent properties of TiO2 thin films which are
subjected to various heat treatments will be presented in
a separate paper [16].
As mentioned in the previous papers [5, 6], Ti 3 + ions
on the surface of the TiO2 electrode are considered to
play an essential role in the decomposition of water
under illumination. In the sol-gel-derived TiO 2 coating
films, Ti ~+ ions are formed by the reduction of thermally
decomposed organic residues. Since 2-ethoxyethanol has
a much higher boiling point (135 °C) than ethanol
(78 °C) or isopropyl alcohol (82 c'C), a large amount of
organic residues may be left in the T3 sample on heating
at 500 °C, which would cause the formation of a larger
amount of Ti 3+ ions. This may also contribute to the
enhancement of photocurrent in the T3 film. The higher
concentration of Ti 3+ in the T3 sample can easily be
expected from the lowest film resistance among the three
series of samples, because Ti 3+ dominates the resistance.
5. Conclusion
The effects of the additives in the dip coating solu-
tions on the properties of the resultant TiO2 coating
23
films were studied. It was found that the addition of
isopropyl alcohol or 2-ethoxyethanol to ethanolic solu-
tions of titanium isopropoxide significantly influences
the crystallization behaviour, microstructure, and pho-
toelectrochemical properties of the resultant TiO2 film.
Enhancement in the photocurrent of the film was as-
sumed to be caused by an increase in crystallinity, a
decrease in resistance, an increase in surface area and
an increase in the amount of Ti 3+ ions of the as-pre-
pared TiO2 coating films.
Acknowledgments
The authors would like to express their sincere grati-
tude to the Asahi Glass Foundation for Industrial
Technology for the financial support. This work was
also supported in part by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Science and
Culture, Japan.
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