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K.H. LEE
Surface Engineering Department, Korea Institute of Machinery & Materials, 66 Sangnam-Dong,
Changwon, Kyungnam 641-010, Korea
J.W. PARK
Division of Materials Science and Engineering, Hanyang University, Seoul 133-791, Korea
Y.K. LEE
Division of Information and Communication Engineering, Science and Engineering Research Institute,
Uiduck University, Kyongju 780-713, Korea
Abstract. The peroxo titanic acid solution was successfully prepared using titanium trichloride as a precursor.
The basic properties of the TiO2 film prepared by the solution were investigated in view of phase change, bandgap
energy, crystalline size etc. The film displayed amorphous TiO2 at room temperature, anatase above 281 C and
a mixture of anatase and rutile at 990 C. The crystalline size increases with annealing temperatures, while the
bandgap energies decrease due to the quantum size effect and the formation of rutile phase which has low bandgap
energy. As a result of TG-DTA, it was found that annealing treatment at 990 C for 2 h formed a mixture of anatase
and rutile through three steps: (1) the removal of physically adsorbed water (2) the decomposition of peroxo group
(3) amorphous-anatase or anatase-rutile phase transformation.
Keywords: titanium dioxide, titanium trichloride, peroxo titanic acid solution, properties
1.
Introduction
The formation mechanism of the titanium peroxo complex has been previously investigated by
Muhlebach et al. [1]. However, a study about the formation of TiO2 film using the PTA has been recently
performed by Ichinose et al. [2]. They mainly used
TiCl4 as a precursor for the synthesis of the PTA solution, but so far no study performed using TiCl3 .
Titanium trichloride can easily dissolve into distilled water (neutral pH), while titanium tetrachloride only dissolves into acid solution. Also, titanium
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Lee et al.
Experimental
A titanium trichloride (Aldrich, 10 wt%, 26 cc) was dissolved in distilled water. Then NH4 OH is added to the
solution until final pH is 8.5. The precipitates obtained
through the phase transformation to titanium hydroxide were filtered and rinsed with distilled water several
time to remove impurities. After then, hydrogen peroxide (10 cc) was slowly added to the precipitates in water
(100 cc) to obtain the peroxo titanic acid solution.
The various substrates, such as slide glass, quartz
and silicon wafer, were dip-coated using a prepared
solution. Each substrate was cleaned in acetone for
5 min and rinsed with distilled water prior to coating. A
coated specimen was dried at room temperature for 6 h
and heated to various temperatures up to 990 C with a
heating rate of 10 C/min followed by holding in air for
2 h.
The surface morphologies were observed by a Field
Emission Scanning Electron microscope (FESEM) and
the thermogravimetric (TG) and differential thermal
analysis (DTA) were performed for the as-dried pow-
Figure 1.
3.
The TG-DTA curves for as-dried powder of PTA solution are shown in Fig. 1. The TG-DTA curve shows
two stages of weight loss with an endothermic peak
minimum at 102 C and exothermic peaks maximum at
257 C. These two stages of weight loss are attributed
to the removal of physically adsorbed water and the
decomposition of peroxo group, respectively. Also, a
broad exothermic peak was observed in the range 300
370 C with a maximum 348 C. It is due to the slow
conversion of amorphous phase to anatase form.
To investigate the composition and existence of impurities in the film dip-coated on slide glass, the XPS
analysis was performed as shown in Fig. 2. Some Na
peaks were observed in survey scan, which is caused
Figure 2.
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(A) survey and (B) narrow scans for the TiO2 film heat-treated at 500 C in air for 2 h.
Figure 3 shows the phase change of the film dipcoated on silicon wafer in accordance with annealing
temperatures. The samples calcined below 273 C displayed amorphous phase, while those calcined above
281 C exhibited anatase or a mixture of anatase and rutile, indicating that amorphous-anatase transformation
occurred around 280 C.
The average crystallite size was estimated from the
main peak of the anatase (101) using the Debye
Scherrers formula as [4]:
t = (0.9)/( cos )
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Lee et al.
Figure 3.
XRD patterns showing the effects of heat treatment in phase transformation of the TiO2 film dip-coated on Si wafer.
tal absorption, the dependence of hv on photon energy for indirect transition is given by the expression
[6]:
(hv)1/2 = Ai (hv E g )
where hv is the photon energy, Ai is a constant which
does not depend on photon energy and E g is the band
gap energy. A quantitative evaluation of the bandgap
energy can be performed by plotting (hv)1/2 against
hv and extrapolating the absorption edge to zero as
shown in Fig. 6. It was found that the bandgap energies
Figure 5.
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SEM micrographs showing the change of surface morphologies of the TiO2 film with annealing temperatures.
4.
Figure 6. Determination of the bandgap energies of the TiO2 film
heat-treated under different conditions.
Conclusions
The peroxo titanic acid solution was successfully prepared using titanium trichloride as a precursor. The
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Lee et al.
Manufacturing and Clean Processes of the Korea Science & Engineering Foundation. We thank Dr. M.S.
Won at the KBSI (Busan) and S.G. Lee at the KBSI
(Daegu) for their valuable discussion in XPS and XRD
experiments.
References
1. J. Muhlebach, K. Muller, and G. Schwarzenbach, Inorg. Chem.
9(11), 2381 (1970).
2. H. Ichinose, M. Terasaki, and H. Katsuki, J. Ceram. Soc. Jpn.
104(8), 715 (1996).
3. P. Babelon, A.S. Dequiedt, H. Mostefa-Sba, S. Bourgeois, P.
Sibillot, and M. Sacilotti, Thin Solid Films 322, 63 (1998).
4. L.J. Meng and M.P. Dos Santos, Thin Solid Films 226, 22
(1993).
5. N. Martin, C. Rousselot, D. Rondot, F. Palmino, and R. Mercier,
Thin Solid Films 300, 113 (1997).
6. D. Mardare and A. Stancu, Mater. Res. Bull. 35, 2017 (2000).
7. T.W. Wang, S.K. Zheng, W.C. Hao, and C. Wang, Surface Coating
Technol. 155, 141 (2002).
8. D. Mardare and G.I. Rusu, Mater. Lett. 56, 210 (2002).