December 2002
Materials Letters 57 (2002) 355 – 360
www.elsevier.com/locate/matlet
Influence of calcination temperature on structural and optical
properties of TiO2 thin films prepared by sol–gel dip coating
Dong Jin Kim a, Sung Hong Hahn a,*, Sung Hoon Oh b, Eui Jung Kim b
a
Department of Physics, University of Ulsan, Ulsan 680-749, South Korea
b
Department of Chemical Engineering, University of Ulsan, Ulsan 680-749, South Korea
Received 20 August 2001; accepted 4 October 2001
Abstract
TiO2 thin films were prepared by sol – gel dip coating and their structural and optical properties were examined at various
calcination temperatures. The X-ray diffraction (XRD) results showed that TiO2 thin film calcined at 300 jC was amorphous,
and transformed into the anatase phase at 400 jC, and further into rutile phase at 1000 jC. The phase transformation
temperature has been dependent upon the concentration of catalyst HCl. The crystallite size of TiO2 thin films was increased
with increasing calcination temperature. The micro-particles in the films grew by intra-agglomerate densification below 1000
jC, whereas they grew by inter-agglomerate densification above 1000 jC. The transmittance of the films calcined at 1000 and
1100 jC was reduced significantly in the wavelength range of about 300 – 700 nm due to the change of crystallite phase and
composition in the films. The refractive index of TiO2 thin films was increased with increasing calcination temperature, and the
film thickness and the porosity of TiO2 thin films were decreased.
D 2002 Elsevier Science B.V. All rights reserved.
PACS: 81.20.Fw
Keywords: TiO2 film; Sol – gel dip coating; Calcination temperature; Crystal structure; Surface structure; Transmittance
1. Introduction guide [7] and photocatalyst [8]. A number of methods
have been employed to fabricate TiO2 films, including
Titanium dioxide is commonly used as coating e-beam evaporation [9], sputtering [10], chemical
materials in optical thin films because it is highly vapor deposition [11], and sol –gel process [12]. The
transparent and has high refractive index and chemical sol –gel process is one of the most appropriate tech-
durability in the visible and near-infrared regions of nologies to prepare thin oxide coating. The interest in
the spectrum [1,2]. TiO2 thin films have been widely the use of sol –gel method is due to several advan-
investigated for various optical applications [3] and tages: good homogeneity, ease of composition control,
have attracted considerable attention for optical filter low processing temperature, large area coatings, low
[4], gas sensor [5], ceramic membrane [6], wave- equipment cost and good optical properties [13,14]. In
particular, the sol – gel processes are efficient in pro-
*
Corresponding author. Tel.: +82-52-259-1693; fax: +82-52-
ducing thin, transparent, multi component oxide
259-2330. layers of many compositions on various substrates,
E-mail address:
[email protected] (S.H. Hahn). including glass [3].
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 7 9 0 - 5
356 D.J. Kim et al. / Materials Letters 57 (2002) 355–360
Crystalline TiO2 film exists in three phases: anatase prepared by using titanium tetra-isopropoxide (TTIP,
(tetragonal), rutile (tetragonal), and brookite (ortho- Junsei Chemical Inc.) as starting material, 0.7N-hydro-
rhombic) [1,13], rutile being the most stable of the chloric acid (HCl) as a catalyst, and isopropanol as a
three, and the formation of its phase depends on solvent. Its typical composition was a molar ratio of
starting material, deposition method and calcination TTIP:isopropanol:0.7N – HCl sol’s=1:26.5:1.5. The
temperature. In particular, TiO2 thin films can trans- solution was under continuous stirring in nitrogen
form from amorphous phase into crystalline anatase atmosphere and room temperature, HCl and isopropa-
and from anatase into rutile by calcination. The nol were added to the TTIP and isopropanol solutions.
refractive index of TiO2 films is related to the crystal The viscosity and PH of the prepared TiO2 solution
phase, crystalline size and density of the films [14]. were 1.8 cP and 5.3, respectively.
Several studies on TiO2 films formed by conventional TiO2 thin films were deposited on substrate by
and advanced sol –gel processes have been reported. sol – gel dip coating at a withdrawal speed of 100 mm/
Negishi and Takeuchi [15] prepared TiO2 sol using min. For the measurement of optical and structural
the polyethylene glycol as an additive, and studied the properties of the deposited film, quartz glass (50 20
crystallinity, morphology, and specific surface area of mm) was used as the substrate and it was cleaned with
TiO2 thin films with heat treatment. Nishide et al. [16] solvent and rinsed with distilled water and then blown
used HNO3 as a catalyst to prepare titania sols and with nitrogen gas prior to film deposition. For struc-
TiO2 films in the sol – gel process. As the firing tural properties measurement, Si-wafer substrate was
temperature increases, the transformation from the used. To obtain the desired film thickness (f 300
anatase to the rutile phase occurs and the refractive nm), it was deposited three times and drying was
index of the films increases linearly. These studies repeated at 100 jC for 30 min in vacuum oven. The
indicate that the properties of TiO2 films depend on TiO2 films were calcined in the temperature range of
the process conditions and the material used in the 300 – 1000 jC with increasing temperature rate of 5
process. Nishide and Mizukami [17] studied the effect jC/min for 1 h in furnace.
of ligands on the crystal phase and refractive index of Thin film X-ray diffraction was used for crystal
TiO2 films prepared by complexing agent-assisted phase identification. XRD patterns were obtained with
sol –gel process, and reported that an organic ligand a Philips PW3710 diffractometer using CuKa radia-
can be used to control the crystal structures and tion at 35 kV and 20 mA and the crystallite size of
optical properties of the films. TiO2 and TiO2 – SiO2 films was estimated by the
In general, the preparation conditions of TiO2 thin Scherrer equation. The micro-particle size and mor-
films in a sol – gel process can strongly affect physical phology were analyzed by field emission scanning
properties of the film [13,14]. Therefore, it is neces- electron microscopy (Hitachi S-4200). Optical proper-
sary to study systematically the structural and optical ties of the films deposited on glass substrates were
properties of sol – gel TiO2 thin films according to examined by transmission spectroscopy in the 300- to
preparation condition. In this paper, TiO2 thin films 1000-nm spectral range. The normal incident trans-
were prepared by a sol – gel dip coating process using mittance of the sample was measured by a UV –VIS
titanium alkoxide as a starting material and HCl as a spectrophotometer (HP 8453).
catalyst. The prepared TiO2 thin films were charac-
terized using XRD, SEM and UV –VIS spectropho-
tometry techniques. The influence of calcination 3. Results and discussion
temperature on the structural and optical properties
of the prepared TiO2 thin films was investigated. 3.1. Structural properties
Fig. 1 illustrates the XRD patterns of the TiO2 thin
2. Experiments films calcined for 1 h in air at various calcination
temperatures from 300 to 1100 jC. The XRD results
The coating solutions were prepared by the proce- indicated that the TiO2 thin film calcined at 300 jC is
dure described as follows. The TiO2 solution was amorphous. The anatase peaks appeared at 400 jC
D.J. Kim et al. / Materials Letters 57 (2002) 355–360 357
h is the half diffraction angle of the centroid of the peak
in degree. Any contributions to broadening due to non-
uniform stress were neglected and the instrumental line
width in the XRD apparatus was subtracted. The results
are listed in Table 1. As the calcination temperature
increases, the TiO2 crystallites continue to grow. The
crystallite size of the anatase phase was increased about
four times from 9.6 to 38.2 nm as the clacination
temperature increases from 400 to 1000 jC. The
crystallite size of the rutile phase at 1000 jC was
42.1 nm and increased to 43.8 nm at 1100 jC.
SEM micrographs of the TiO2 thin films calcined
at various temperatures are shown in Fig. 2 and all
films fabricated were uniform. Even though the film
calcined at 400 jC was the anatase phase according to
Fig. 1. XRD patterns of the TiO2 thin films calcined at different the XRD results, crystallinity was not observed in Fig.
temperatures.
2(a) because of the small crystallite size. In Fig. 2(b)
and (c), we can clearly see the crystallinity of the films
resulting from a phase transition from amorphous
calcined at 500 and 600 jC but it is difficult to
phase to the anatase phase. As the temperature
identify the secondary particles in the films at these
increased from 400 to 900 jC, the intensities of the
temperatures. In Fig. 2(d), the film calcined at 700 jC
anatase peaks were increased implying an improve-
is composed of the secondary particles of about 30 –
ment in crystallinity. On increasing the temperature to
40 nm in size. Here, the primary particles comprising
1000 jC, the intensities of the anatase peaks
the secondary particles cannot be identified. As the
decreased, but the rutile peaks appeared. When the
calcination temperature was increased to 800 jC, the
calcinations temperature was increased further to 1100
film (Fig. 2(e)) shifted into the agglomerated state
jC, anatase peaks nearly disappeared while the inten-
whose size reached about 50– 70 nm as a result of
sities of the rutile peaks greatly increased. According
densification. Fig. 2(f) shows that the film has been
to Ref. [15], the anatase-to-rutile phase transformation
densified by calcination at 900 jC due to the elimi-
took place at temperatures of 600– 800 jC. In this
nation of intercrystallite pores. The size of secondary
work, the phase transformation occurred at 1000 jC.
particles increased to about 70 – 100 nm. It is interest-
This discrepancy may be due to the difference in
ing to note in Fig. 2(g) and (h) that the size of
crystallite structure and size of TiO2 films. Hashimoto
secondary particles increased considerably to 150 –
et al. [18] reported that rutile peaks appeared at 650
300 nm at temperatures of 1000 and 1100 jC.
jC when diethanolamine (DEA) was used as a cata-
lyst while rutile peaks did not appear at 800 jC when
HNO3 was employed in the same capacity. Therefore, Table 1
crystalline phase transition temperature depends on a Crystallite size of the TiO2 thin films calcined at various temper-
catalyst used in the sol preparation. atures for 1 h
The crystallite size of TiO2 thin films can be Calcination temperature (jC) Crystallite size (nm)
deduced from XRD line broadening using the Scher- Anatase Rutile
rer equation [19]. 400 9.6
500 16.1
Kk 600 16.8
L¼ ð1Þ
bcosh 700 18.6
800 24.5
where L is the crystallite size of TiO2 thin films, K is a 900 29.1
constant ( = 0.94), k is the wavelength of X-ray 1000 38.2 42.1
1100 43.8
(CuKa = 1.5406 Å), b is the true half-peak width, and
358 D.J. Kim et al. / Materials Letters 57 (2002) 355–360
Fig. 2. SEM micrographs of TiO2 thin films calcined at various temperatures for 1 h: (a) 400 jC; (b) 500 jC; (c) 600 jC; (d) 700 jC; (e) 800 jC;
(f) 900 jC; (g) 1000 jC; (h) 1100 jC.
D.J. Kim et al. / Materials Letters 57 (2002) 355–360 359
Furthermore, the secondary particles became highly to rutile phase. Moreover, the non-stoichiometric film
densified and had a non-spherical shape. This result would be formed at higher calcination temperatures.
indicates that sintering of the nanocrystalline TiO2 We observed that if the concentration of HCl was
particles is accelerated at higher calcination temper- increased to more than 0.7 N, this phenomenon
atures. This may be related to a change in the surface appeared at a lower calcination temperature.
structure of films by crystal phase transformation, The refractive index of the TiO2 thin films pre-
which was confirmed by the XRD results [20]. pared at various calcination temperatures was calcu-
lated from the measured transmittance spectrum. The
3.2. Optical properties evaluation method used in this work is based on the
analysis of the transmittance spectrum of a weakly
Fig. 3 shows the UV – VIS spectra of TiO2 thin films absorbing film deposited on a non-absorbing substrate
calcined at various temperatures for 1 h in wavelength [21]. The refractive index n(k) over the spectral range
range 300– 1000 nm. The bands due to the interference is calculated by using the envelopes that are fitted to
color of the film appeared in the wavelength range the measured extrema:
350 –800 nm. The amplitude of interference spectra rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
increased with increasing calcination temperature. nðkÞ ¼ S þ S 2 n20 ðkÞn2s ðkÞ ð2Þ
These results show that the refractive index of TiO2
thin films is increased while the film thickness is
decreased. The absorption edges of the rutile TiO2 thin 1 2
films prepared by calcination exceeding 1000 jC for 1 s¼ ðn ðkÞ þ n2s ðkÞÞ
2 0
h (as shown in Fig. 3(g) –(h)), were shifted to at longer
wavelength range with the phase transformation from Tmax ðkÞ Tmin ðkÞ
þ 2n0 ns ð3Þ
anatase to rutile. This shift is ascribed to the difference Tmax ðkÞ Tmin ðkÞ
in band gap energy of the TiO2 thin films by the anatase
to rutile phase transformation [18]. It is remarkable to where n0 is the refractive index of air, ns is the
note in Fig. 3(g) and (h) that transmittance of TiO2 thin refractive index of film, Tmax is the maximum enve-
films at temperatures above 1000 jC was reduced lope, and Tmin is the minimum envelope. The thick-
considerably in wavelength range of about 300 – 700 ness of the films was adjusted to provide the best fits
nm. The films turned out to be translucent at these to the measured spectra. In this study, all the deposited
higher temperatures. This is due to the absorption films are assumed to be homogeneous.
resulting from the phase transformation from anatase The property of the thin films is calculated using
the following equation [22]:
n2 1
Porosity ¼ 1 2 100ð%Þ ð4Þ
nd 1
where nd is the refractive index of pore-free anatase
(nd = 2.52 [23]), and n is the refractive index of the
porous thin films. Fig. 4 shows the resultant refractive
index and porosity of the TiO2 thin films calcined from
400 to 900 jC. It is seen that the refractive index
increased from 2.00 to 2.35 with increasing calcination
temperature and the porosity decreased from 44% at
400 jC to 15% at 900 jC. This is due to film densifi-
cation and pore destruction in films during calcination.
Note in Fig. 4 that the refractive index of the films is
significantly increased with increasing temperature
Fig. 3. UV – VIS spectra of TiO2 thin films calcined at various over 700 jC. At a temperature exceeding 1000 jC,
temperatures for 1 h. where the anatase-to-rutile phase transformation takes
360 D.J. Kim et al. / Materials Letters 57 (2002) 355–360
shrinkage and densification of the films. From this
study, we successfully fabricated optical materials in
thin films, having desired structural and optical proper-
ties by sol – gel dip coating using the titanium alkoxide
as a starting material.
Acknowledgements
This work was supported by grant No. (2001-1-
11100-008-2) from the Basic Research Program of the
Korea Science and Engineering Foundation. The
authors thank Korea Basic Science Institute (Taegu
Fig. 4. Refractive index and porosity of TiO2 thin films calcined at Branch) for XRD and SEM measurements.
various temperatures for 1 h at 550-nm wavelength.
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