"

:~m! ,;'t' <':i

Thin Solid Films 283 (1996) 188-195

Photoelectrochemical properties of TiO2 coating films prepared using

different solvents by the sol-gel method
Toshinobu Yoko, Lili Hu 1, Hiromitsu Kozuka, Sumio Sakka
Institutefor Chemical Research, gyoto University Uji, Kyoto-Fu 611, Japan
Received 16 December 1994; accepted 30 October 1995

Abstract

The effects of the soNent used for preparing a coating solution on the photoelectrochemical properties of the sol-gel derived Tie2 film
electrodes have been investigated. Three series of T i e 2 film electrodes were prepared from three different coating solutions, in which ethanol,
ethanol-isopropyl alcohol and ethanol-2-ethoxyethanol were used as a solvent, and Ti (OC3H7 /) 4as a source of ' r i o 2. The photocurrent of each
series of 3 ~O2film electrodes increased with increasing film thickness up to about 1 ILmand became almost invariant beyond that, indicating
that a film thickness of about I t.~m is required for achieving the highest efficiency. The photoelectrochemical performance of Tie2 film
electrodes was strongly dependent on the heat-treatment conditions as well as on the composition of the starting solutions. The results obtained
were mainly explained in terms of the electrical resistance of the Tie2 film electrodes.

Keywords: Crystallization; Titanium oxide; Electrochemistry; Semiconductors

1. Introduction ence the crystailisation behaviour, porosity and microstruc-

A number of works [ 1 ] have been performed on a TiO~
semiconductor electrode for photoelectrochemical solar
energy conversion since Fujishima and Honda [2] demon-
strated that TiOz has both chemical and photoelectrochemical
durability when used as a photoanode for decomposition of
water, We have first made an attempt to apply the sol-gel
coating process to th~zpreparation of TiO2 coating film elec-
trodes [ 3-5]. The sol-gel coating technique is favorable for
preparing photoeleclxodes of wet-type solar cell as it provides
(1) porous films with large specific surface area, and (2)
film electrodes of large size homogeneously doped at a
molecular level with either organic molecules or meta| ions.
Here, it is noteworthy that O'Regan and Gr~itzel .[6] have
recently made a high-efficiency solar cell using dye-sensi-
tized Tie2 films prepared by the sol-gel method.
It is known [7 ] that properties of the sol-gel derived films
are strongly dependent not only on the composition of the
coating solutions, but also on the preparation conditions
including the kinds of starting materials and solvents, solution
preparation sequence, ageing temperature and time, and firing
~mperature. In the previous paper [8], it was found that the
kinds of solvent used in coating solutions appreciably influ-
' On leave from: Shanghai Institute of Optics and Fine Mechanics, Aca-
demia Sinica. Box 8216, Shanghai, People's Republic of China.
0040-60901961515.00 © 1996 Elsevier Science S.A. All rights reserved
SSD10040-6090(95)08222.0
ture of the sol-gel derived Tie2 coating films. Based on
photocurrent and impedance measurements, in the present
paper, we report on the effects of solvent on the photoelec-
trochemical properties of three series of Tie2 sol-gel coating
films prepared from three kinds of coating solutions.
2. Experimental
2.1, Preparationof TiO2coatingfilms
Three kinds of coating solutions, TI, T2 and T3 sols, were
prepared using ethanol, ethanol mixed with isopropyl alcohol
and ethanol with 2-ethoxyethanol as solvents, respectively.
Their chemical compositions are listed in Table 1. Tie2 thin
films prepared from T1, T2 and T3 sols are hereafter called
TI, T2 and T3 respectively. A more detailed description of
solution preparation and film formation processes appears
elsewhere [ 8].
Nesa silica glasses of 20× 35 × 1 mm3.in size were used
as substrates for Tie2 film electrodes. In order to increase the
film thickness the dip-coating-firing process was repeated
5, 7, 10 and 15 times. The coating film was heat-treated at
500 °C for 10 min after each dipping. 5 time deposited Tie2
samples were subjected to further heat-treatment at 500, 600,
700, 800 and 900 °C for various periods of time.
 7". Yokoet al. / ThinSolidFilms283 (1996) 188-195 189

Table 1
Compositionsof starting solutions

Composition (mole)

Sol Ti(OC3HT~)a CzH~OH iC3HvOH C2HsOC2H4OH HCI H20 TiOz" (wt.%)

TI 1 9.2 - - 0.15 I 10.8

T2 1 5.3 3 - 0.15 I 10.8
T3 1 8.2 - 0.5 0.15 I 10.8

"Equivalent oxidecontent of TiO2in sols.

2.2. X-ray diffraction 2.3. Photocurrent measurements

Crystallisation behaviour of the sol-gel derived TiO2 coat-
ing film was examined by X-ray diffraction using Cu K,~ The photocurrent-potential curves of the TiO2 film elec-
radiation. trodes in contact with a buffer solution of pH 7 containing
0.2 M Na2B4OT, 0.14 M H2SO4 and 0.3 M Na2SO4 were
obtained with a potentiostat (Model HG-501 of Hokuto
a: 5 timeo Denko Co. Ltd., Tokyo). A 500 W xenon lamp (Ushio Denki
(A) ~40 b: 7 t i n
c 10 tines Co. Ltd., Tokyo) was used for illuminating the film elec-
~30 d: 15timu ¢
trodes. All photoeleetrode areas were 0.196 cm e. Action
spectra were measured over a wavelength range from 300 to
450 nm by using a xenon lamp and a monochromator (Shi-
madzu, Model SPG-100S).

I I
~..~'~ , dark 2.4. Impedance analysis
-1.5 -S.O -0.6 [o o~6 s~o 1.6 9..0
In order to evaluate the resistance and space charge layer
g/V ve SCl~ capacitance of the TiO2 film electrode in the dark and under
e illumination, impedance analysis was performed in the same
(B) 50
solution (pH 7 ) at I kHz, using a frequency response analyzer
il 40 (Model FRA-5090 of NF Circuit Block Co. Ltd., Tokyo)
i1 combined with the potentiostat. It should be noted here that
the impedance analysis under illumination is considered not

1" tO
/
// b: 7 tines
e:10 time,
& 15 times
to give the reliable aata in a certain case.

3. Results
dark
t / ' ~ --

-1,5 -1 0 0.5 1.0 l,G 2.0

S:
3.1. Variation of photocurrent with film thickness
g / v ve 8cg
Fig. 1 shows the photocurrent-potential curves of as-pre-
(12) pared T1, T2 and T3 film electrodes as a function of the
50 e
number of dippings. The average thickness of a fired film
with one dipping was found to be 0.081 p~m, 0.115 Ixm and
0.085 p~m for T1, T2 and T3 samples, respectively [8]. It is
obvious that the photocurrent strongly depends on the

i '° 3O

20 /]"
//
b: I times
c: to tin
d:lG times
thickness.
As shown in Fig. 2, the photocurrents in the plateau region,
nieasured at 2 V vs. SCE, for as.prepared T1, T2 and T3
1o~ samples increase with the number of dippings, and attain
maximum values of 28, 52 and 50 mA cm -2, respectively,
t J , , ,~dark
t after 10 dippings corresponding to the film thickness of about
-1,5 -1,0 -0,5 [0
1.0 1,5 0.5
2.0
1 ttm. This result shows the influence of the coating solution
I
g/V voseg
used on the saturation photocurrent of the respective TiOz
Fig. 1. Variationsof the photocurrent, measuredat 2.0 V vs. SCE, with the
numberof dippings in as-preparedTI (a), T2 (b) and T3 (c) samples. samples, as it is larger for T2 and T3 than for T1 sample.
190 7". Yoke etal,/Thin Solid Films 283 (1996) 188-195

60 • . • " • i

(A) 50
50 ?1 H ?O0'C
40
~ 4o
3O
so 600'C

50
P,
.~ 40 r
, ~ , __._,. dark
30 -1.5 -1.0 -0.5 i0 0.5 l,O 1.5 ~.0
T2
10 B/V vs 8CB
0 l a w t ! . . . . i

50 (n) ~ so
40' "~ 40
600'C
30 ~ 500'C
./'7 ~ 700'C
90 T3 ~ 3O ///_~- soo,c
10 I
0
i t . . . . i
30
10 15
Number of dippings
Fig, 2. Relations between the saturated photocurrent, measured at 2.0 V vs. dark
SCE, and the number of dippings in as-prepared T i ( a ), T2 (b) and T3 (c)
samples. -1.5 -I.0 -0.5 0.5 1.0 1,5 3.0
g / v vs SCB

~
3.2. Variationof photocurrent with heating temperature (c)
500'C
50
Fig. 3 shows the photocurrent-potential curves of five- 600'C
time deposited T1, T2 and T3 samples as a function of heating
temperature. As can be seen in Fig. 4 the heating temperature
dependence of the photocurrent measured at 2.0 V vs. $CE
is different for each sample. For the TI sample, the photo- i,o 30
900 C
current increases with increasing heating temperature, and 2O
reaches a maximum value of 48 mA cm -2 at 800 °C. The T2
sample shows the largest photocurrent of 40 mA cm-2 at
600 °C. However, the T3 sample shows a slight decrease of , , ,___... dark
photocurrent up to 800 °C and a sharp decrease at 900 °C.
-l.0 -0,5 I0 0.5 L0 t.s s.0
Ten-time deposited TI, "1'2and I"3 samples were also sub- I

jected to heat-treatments at 500, 600 and 800 °C for various
periods of time, although the results are not shown here. The
largest photocurrents were obtained under the following con-
ditions: T1,800 °C, 10 min; T2, 600 °C, 30 rain; '1"3,500 °C,
20 min. The corresponding maximum photocurrent values
for TI, T2 and "1"3samples were 50, 54 and 56 mAcm -2,
respectively, as listed in Table 2. In the following these sam-
ples, which were subjected to heat-treatment under optimum
conditions to give the largest photocurrent, are called the
"optimized sample".
3.3. Electrical resistance of TiOzfilms
Fig. 5 and Fig. 6 show the variations of the electrical resis-
tance of TiO2 film electrodes, measured in the dark and under
illumination, with the number of dippings and heating tem-
perature, respectively. In all cases, the film resistance is lower
g/Y ve 8Cg
Fig. 3. Photocurrents of five-time deposited TI (a), T2 (b) and T3 (c)
samples as a function of heating temperatures for 10 rain.
under illumination than in the dark due to the photoproduction
of carriers. As seen in Fig. 5, the film resistance decreases
with the number of dippings and becomes almost invariant
over 10 dippings for all samples.
Comparing Fig. 5 with Fig. 2, it is obvious that the film
resistance and the photocurrent of the TiO2 samples vary in
the opposite way to each other with dipping time. Fig. 6
indicates that TI, T2 and T3 samples get the smallest film
resistance at 800, 600 and 500 °C, respectively. The film
resistance of TI sample decreases with heat-treatment tem-
perature up to 800 0(2, and then drastically increases. The T2
sample shows a minimum resistance at 600 °C. The film
resistance of the T3 sample seems to increase continuously
 T. Yokoet al. I ThinSolidFilms283 (1996)188-195 191

60 | , i i i Vco the flatband potential, V the bias potential vs. SCE. kT/q
T1 is frequently ignored due to the accuracy of this technique
40 (-I-0.05 V) [ 1]. The flatband potential and donor density
are obtained from the intercept and the slope of the C~ 2 versus
V plot respectively.
20
Table 2 summarises the flatband potential and donor den-
I I I I I
sity values corresponding to the TI, T2 and T3 samples.
0 Noticeable flatband potential shifts of the order of 0.5 V
T2 towards positive potentials were observed for these sol-gel
)zm
40 derived TiO2 film electrodes upon illumination.
There is a significant difference in donor density between
20 TiO2 samples prepared under different heat-treatment con-
.Ira
ditions as seen from the second last column of Table 2.
I I I I I Among the as-prepared samples, the T1 sample has the lowest
0
donor density of 0.66 × 1020 c m - 3 and T3 sample the highest
donor density of 1.79 × 1020 cm-3. The donor densities of
40
the "optimized samples" increased by more than twice in all
cases compared with the as-prepared samples.
20
3.5. Action spectra of TiOz samples
I I I I I
0
500 600 700 800 900 The action spectra of ten-time deposited, as-prepared TI,
Tempenture/*C T2 and T3 samples are shown in Fig. 7. Note that they were
Fig. 4. Relationsbetween photocurrentand heating temperaturesin TI, "1"2 taken at a bias potential of 1.3 V vs. SCE to avoid the influence
and T3 samples.The photocurrentswere measuredat 2.0 V vs. SCE. of the dark current which emerges at more than 1.5 V vs. SCE
as seen from Figs. 1 and 3. Although the shapes of the action
with temperature. By comparison of Fig. 4 and Fig. 6, it is spectra are quite similar to each other, some differences can
also found that the decrease of photocurrent with heat-treat- be recognized. The peak positions are shifted to longer wave-
ment temperature is just opposite to that of the film resistance, lengths from about 340 nm in the TI sample to 345 nm in the
i.e. the increase (decrease) of film resistance leads to the T2 sample and 350 nm in the T3 sample. It is also seen that
decrease (increase) of photocurrent. for the T2 and T3 samples the photocurrent response is
observed to extend up to about 420 nm, while it ends at
3.4. Flatband potential and donor density 400 nm for the T1 sample.
The optical bandgap energy Eg of the interband transition
The flatband potential and donor density of a semiconduc- can be estimated from the following equation [ 10],
tor electrode can be determined by the Mott-Schottky equa-
(lhv),,f A(hv_ Er,) (2)
tion [ 1 ]:
where I is the photocurrent, hu the photon energy of the
2 V incident light and A the constant dependent on the bias poten-
C~Z=-q~d88o ( - V r b - ~ (1)
tial. m = 1/2 and 2 for indirect and direct optical transitions,
where Cs is the capacitance of a space charge layer, q the respectively. The relations between (lhv)" and hv, which
electronic charge, Nd the donor density, ¢ the permittivity of were obtained from the data in Fig. 7, are shown in Fig. 8. It
TiO2, which equals 82.5 [9], eo the permittivity of vacuum, is obvious from Fig. 8 that a linear relationship holds for

Table 2
Photocurrents, flatbandpotentialsand donordensitiesof 10-timedeposited,as-preparedand optimizedTiO2filmelectrodes

Flatband potential (V vs. SCE) Donor density Bandgap energy

Samples Photocurrent
( x 10~°c m -3) (eV)
tmAcm -2)
Dark a Light b Ac

- 1.00 - 0.50 0.50 0.66 3.10

TI (as-prepared) 28 1.24 3.03
T2 (as-prepared) 52 - 1.I0 - 0.58 0.52
- 1.07 - 0.60 0.47 ! .79 3.03
T3 (as-prepared) 50 1.80 2.98
TI (800 °C, 10 min) 50 - 1.00 - 0.56 0.44
1.00 - 0.60 0.40 4.82 2.98
T2 (600 °C, 30 min) 54 -

3.28 3.03
T3 (500 °C, 20 rain) 56 - 1.00 - 0.58 0.42

C A = l ' - b I.
192 T. Yoko et al. / Thin Solid Films 283 (1996) 188-195

i I i I I
i . . . . i . . . . i

400 c 3OO T1
. ~ Dark~_
200 200 ~
Lighte -
l I I I I I I I I I
100
40O T2
\
1 300
200 T2
.ram
1 Light
_e o i ~ i i . , , , I
~200
400 T3 \

200 ^ Dark ~.
0 , . . . . . . Light
300 T3
10 15
Humberofdippings 200 ~
Fig. 5. Plots of the film resistance measured for the dark and under illumi-
nation at 0 V vs. SCE against the number of dippings for T1, T2 and T3
samples. 100
! ! ! ! i

6OO 0 -
800 400 500
400 Wavelenftb/nm
Fig. 7. Action spectra, measured at 1.3 V vs. SCE. of as.prepared, 10-time
deposited TI, T2 and T3 samples.
2O0 - - o ~ Light

0 4. Discussion
600 T2
4.1. Effects of film thickness on the photocu,,em
'1 4oo
The thickness of a semiconductor film electrode has been
~• IO0 found to be critical to the cell performance of a wet type solar
cell [3]. First, it must exceed at least the width of the space
0 I I I I i
charge layer, which is formed when the electrode is brought
600 T3 into contact with an electrolyte. Otherwise, the sufficientband
bending in the space charge layer would not be achieved,
400 Dark/o, leading to a lowering of the quantum efficiency. The same
situation may also occur if the density of majority carriers in
100 the film is too low to generate a high electrical field at the
space charge layer. Such a situation may be encounteredwhen
the thickness is extremely small and/or the density of major-
0 I I I I I

ity carriers is extremely low. However, it is of value to note

500 600 700 800 900
that a thicker film than required gives rise to a voltage drop
iemperature/'C across it, if the film resistance is high. So the film electrode
Fig. 6. Film resistance measured in the dark and under illumination at 0 V
vs. SCE of five-time deposited TI, T2 and T3 samples as a function of heat- may have an optimum thickness which ensures the best
treatment temperature for l0 min. energy conversion efficiency.
As shown in Fig. 5, the film resistance of as-prepared T1,
m ffi 1/2 while does not for m-- 2. Therefore, the as-prepared T2 and T3 samples decreased with the number of clippings,
T1, T2 and T3 samples ate indirect bandgap semiconductors. i.e. the film thickness, and beyond 10 dippings became invar-
Their bandgap energies are listed in the last column of iant with the T1 and T3 samples and slightly increased with
Table 2 together with the results for the optimized samples. the T2 sample. This dependence of film resistance with film
 T. Yoko et al. / Thin Solid Films 283 0996) 188-195 193

1.0 to electrical conduction. Therefore, the present result indi-

cates that a thickness of more than 1 Ixm is required for
achieving sufficient band bending because of the low density
I of carriers.

0.5 4.2. Effects of heat-treatment on the photocurrent

It was found from Fig. 2 that the photocurrent of the sol-

0 The heating temperature at which a maximum photocurrent
3.0 3.2 3.4 3.6 hv/eV
411
(b) T2 (e) T3
1.0 0 [8], the T1, T2 and T3 samples differed from one another
m--] '2 n'I/~/
.5
0.5
3.0 8,2 3.4 3.6 hu/eV 3.0 8,2
Fig. 8. Plots of (llw)" against hu in as-prepared TI, T2 and T3 samples.
thickness is also found with the photocurrent in Fig. 2, indi-
cating that the film resistance primarily governs the photo-
current in the TiO2 film electrode.
Here, it is interesting to point out that the film resistance
decreases with the film thickness up to a certain value (about
l~m) as observed for all series of samples prepared in the
present study. Such a behaviour is, however, just opposite to
what was to be expected: ( 1) ~ .~pacecharge layer larger than
the film thickness and (2) the inerense of the majority carrier
density with film thickness could explain this behaviour. The
width, ,:, of the space charge layer can be estimated by the
equation [ 1],
f2 \1/2
where % is the baud bending in volts and the rest have the
same meanings as above. For e = 82.5, ~ = 1-2 V and
Na = 10~°--102' cm- 3, d is of the order of 0.01 I~m, which is
much smaller than the film thickness. So the first possibility
stated above can be ruled out. Taking into account the exper-
imental fact that the film resistance becomes almost constant
over a certain thickness, the second one may be more feasible.
That is, a diminution of the majority carriers density would
cause a low band bending when the film is brought into
contact with the electrolyte, which results in a higher film
resistance, since the space charge layer does not contribute
gel derived TiO2 film electrodes prepared from T1, T2 and
T3 sols strongly depends on the heat-treatment temperature.
is attained significantly differs from sample to sample. The
photocurrent of the TiO2 film electrodes is considered to be
dominated by several factors, such as crystallinity, specific
surface area and film resistance [ 1,4]• As found previously
in crystallization behaviour, microstructure and surface
st~eture.
For example, the ratios of the peak area of the anatase
( 101 ) line of TiO2 films heated at temperatures from 500 °C
to 800 °C to that of the film heated at 900 °C obtained from
the X-ray diffraction data previously reported [8] are listed
in Table 3. These ratios are assumed to be a measure of film
crystallinity. It can be seen from these values that the crys-
tallization of the T2 and T3 samples into anatase is completed
at 700 °C, while a higher temperature is needed for sample
3.4 3.6hJeV T1. This result well corresponds to those data pre"iously
reported [ 8 ].
With respect to the heating temperature dependence of the
photocurrents (see Fig. 2), the crystallinity seems not to be
a dominant parameter determining photocurrent intensity,
especially for the T2 and T3 samples, as the photocurrent
decreases with increasing heating temperature. It seems,
therefore, reasonable to assume that the decrease of film resis-
tance does contribute more significantly to the photocurrent
than the increase of crystallinity. It is well known that a too-
high bulk resistance leads to low quantum efficiency due to
a decrease in the electric field gradient across the depletion
layer. The same result can be obtained with a low bulk resis-
tance due to the thin space charge layer [4]. Accordingly, an
optimum bulk resistance must be obtained in order to achieve
the highest quantum efficiency [4,11,121.
On the other hand, it is believed that the presence ofTi 3+
ions in a TiO2 semiconductor electrode makes a great contri-
bution to their photoelectrochemical properties, as far as Ti 3 +
Table 3
Ratios of ~:ray diffraction peak area of anatase ( 101 ) line of TiO~ films
heated from 500 to 800 oC to that heated at 900 oC
Sample Heating temperature (°C)
500 600 700 800 900
TI 0.51 0.63 0.7 0.87 1.0
'1"2 0.57 0.68 ! .0 1.0 1.0
T3 0.67 0.72 1.0 1.0 1.0
194 1", Yolu~et al. / Thin Solid Films 283 (1996) 188-195
ions dominate both the photoelectrochemical reactions at the
surface and bulk electrical conductivity by the formation of
donor levels in the conduction band of TiO2 [ 1,4,13]. Ti 3+
ions in the present sol-gel derived films are considered to be
exclusively produced by the reduction of Ti4 + by undecom-
posed organic residues or unburned free carbons during heat-
ing [4]. Therefore, the concentration of Ti3+ ions produced
in the film depends on the porosity, the type of organic groups
remaining in the gel film and the heat-treatment conditions,
such as heating temperature and time. A long-time or a high-
temperature heating could lead to the reoxidation of Ti 3+ to
Ti4+, and consequently an increase of the resistance.
It is also interesting to note that a maximum photocurrent
value is practically reached for all even though heat-treatment
conditions are different. This fact means that it is possible to
control the maximum heating temperature in the range from
500 to 800 °C can be chosen to produce a maximum photo-
current by adequately selecting the solvent of the coating
solution.
4.3. Flatband potential
In the previous studies [4,14], the sol-gel derived TiO2
film electrodes were found to show a flat band potential shift
towards positive potentials as large as 0.5 V upon illumina-
tion. This shift was also found to depend on the solution pH,
illuminating light intensity and so on. As can be seen in Table
2, the shift of flatband potential caused by illumination can
be estimated at about 0.5 V for the as-prepared samples and
about 0.42 V for the optimized samples, respectively. The
shift of flatband potential upon illumination, which is caused
by hole trapping at the surface states, can be estimated from
the following equation [ 1,15,16],
A V., = I V . , - V ~, l = qN,.J C . (4)
where V~ and ~ are the fiat band potentials in the dark and
under illumination, respectively, N~sis the density of surfaces
states and Ca is the Helmholtz layer capacitance. If one
assumes that the value of Ca ranges from 0.1 to 1 × 102 ixF
era-2 and A Vro--0.5 V, N~ can be estimated to be of the
order 0.3-3 × 10~4cm -2, a value one or two orders of mag-
nitude larger than that corresponding to TiO2 single crystal.
Such a large density of surface states can be attributed to the
porous nature of the sol-gel derived TiO2 films.
4.4. Optical bandgap
In the previous work [4], we reported that in the sol-gel
derived TiO2 film of anatase phase an indirect optical tran-
sition with a bandgap energy of 3.03 eV was prevailing, while
the rutile film showed both an indirect bandgap of 2.92 eV
and a direct bandgap of 3.13 eV. The as-prepared T 1, T2 and
T3 anatase films prepared in the present study are found to
have an indirect bandgaps of 3.10, 3.03 and 3.03 eV, respec-
tively, in accordance with the previous results. Therefore, we
can say that the band gap energy of sol-gel derived anatase
TiO2 films does not depend on crystailinity.
There is a slight difference in the action spectra of the as-
prepared TI, T2 and T3 samples as shown in Fig. 7. Photo-
current rises at about 400 nm in TI sample, while it rises at
about 410 nm in the T2 and T3 samples. The maximum value
of photocurrent in the T1 sample is lower than those of the
T2 and T3 samples. The shifts of peak position and current
,ise towards longer wavelengths may be ascribed to the
improved crystailinity, as far as crystallinity increases in the
order T1 <1"2 <T3 from Table 3.
5. Conclusions
The dependence of photoelectrochemical properties of
TiO2 thin film electrodes prepared by the sol-gel method on
heat-treatment conditions and number of dip coatings has
been investigated. Ethanol, ethanol mixed with isopropyl
alcohol and ethanol with 2-ethoxyethanol were used as sol-
vents, and Ti(OC3HT~)4 was used as the starting material. It
was found that the photocurrents of the sol-gel derived TiO2
film electrodes are significantly dependent on the solvents
used via film thickness, crystallinity, surface area and the
density of Ti 3+ donor ions. A film thickness of about 1p.m
was found to be required for achieving the highest efficiency.
The best beat-treatment conditions to give a maximum pho-
tocurrent changed from series to series (800 °C for 10 rain
for series T1,600 °C for 30 rain for series T2 and 500 °C for
20 min for series T3) although the maximum photocurrent
was almost the same for the three series. A shift of flatband
potential of about 0.4--0.5 V towards positive potentials upon
illumination was observed for all series of TiO2 film elec-
trodes. An indirect transition with TiO2 bandgap energies of
3.10 eV for T1,3,03 eV for the T2 and T3 samples was found.
Acknowledgements
The authors would like to express their sincere gratitude
to The Asahi Glass Foundation for Industrial Technology for
the financial support.
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