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Journal of Sol-Gel Science and Technology 31, 6772, 2004

c 2004 Kluwer Academic Publishers. Manufactured in The United States.




Preparation and Characterization of Peroxo Titanic Acid Solution


Using TiCl3
C.K. LEE, D.K. KIM, J.H. LEE, J.H. SUNG AND I. KIM
Department of Metallurgical Engineering, Dong-A University, #840 Hadan 2-dong,
Saha-gu, Busan 604-714, Korea
iskim@daunet.donga.ac.kr

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

Titanium dioxide has attracted much attention because


of its wide range of industrial applications. Many
coating solutions have been developed. Among these,
the peroxo titanic acid solution (PTA) is of great interest because it has neutral pH and low material
cost.
To

whom all correspondence should be addressed.

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.

tetrachloride released large amount of chlorine gas


when it was exposed in air. At this point, titanium
trichloride is considered to be a good precursor for the
preparation of the PTA.
In this study, the PTA solution was prepared using
TiCl3 as a precursor and the basic properties of the film
dip-coated on various substrates were investigated.
2.

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.

TG-DTA curves for as-dried powders at room temperatures.

ders at room temperature using a TG-DTA analyzer


(Shimazu TA-50WSI) with a heating rate of 10 C/min
in air. The phase change of the film with annealing temperatures was investigated by a X-ray diffractometer
(Philips PW 3710) and the absorbance of the film was
measured by a UV-Visible spectrometer. XPS analysis
was carried out to confirm the presence of impurities
and identify the chemical states of the film. The binding
energy values were calibrated with the C1s line of adventitious carbon at 284.60 eV. Before experiments, the
surface of specimen was argon-ion sputtered (energy
5 KeV) for 20 s.

3.

Results and Discussion

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

Preparation and Characterization of Peroxo Titanic Acid Solution Using TiCl3

Figure 2.

69

(A) survey and (B) narrow scans for the TiO2 film heat-treated at 500 C in air for 2 h.

by the diffusion of Na in slide glass, but the others


are only composed of Ti and O peaks. The Ti(2p3/2)
peak and Ti(2p1/2) in Fig. 2(B) are positioned around
458.35 eV and 464.05 eV, respectively, and difference
between two peaks is within 5.7 0.05 eV, which is
characteristic of Ti in TiO2 [3]. In this study, the oxides containing Ti3+ , such as Ti2 O3 , are expected to be
partially formed because titanium trichloride as a precursor is used. However no oxides containing Ti3+ was
observed. This fact indicates that Ti3+ is fully oxidized
to Ti4+ due to air exposure during reaction in solution
or due to the post heat treatment in air.

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.

where t is the crystallite size of TiO2 film, is the


wavelength of the copper K radiation (1.5406 A),
is the full-width at half-maximum (FWHM) of the
X-ray line, and is Braggs diffraction angle. It has
been well known that the diffraction line width is affected by strain, defects, surface tension, and instrumental broadening effects. In this study, instrumental
broadening was estimated with a standard silicon sample and taken into account in the crystallite size estimation. However, any contributions to line broadening
except instrumental line broadening effects were neglected. The crystallite size increases with annealing
temperatures as shown in Fig. 4. Figure 5 shows the
surface morphologies of the TiO2 film with annealing
temperatures. The grain size at 710 C and at 990 C
displayed 50 nm and 100 nm, respectively, while
the average crystallite size measured by the Debye
Scherrers formula at same conditions exhibited 43 nm
and 55 nm, respectively. This fact indicates that the
DebyeScherrers formula induce some errors in measuring the absolute values of the crystallite size.
For wavelength close to value where the scattering
losses are dominated by the fundamental absorption,
the absorption coefficient can be calculated using a
following relationship [5]:
= ln(1/T )/d
where d is the thickness of the film and T is the
optical transmittance. In the vicinity of fundamen-

Figure 4. Change of average crystallite size with annealing temperatures.

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

Preparation and Characterization of Peroxo Titanic Acid Solution Using TiCl3

Figure 5.

71

SEM micrographs showing the change of surface morphologies of the TiO2 film with annealing temperatures.

of the film decreased with annealing temperatures. This


is ascribed to the quantum size effects [7] and the formation of rutile phase [8] which has lower bandgap
energies than anatase at high temperature as shown
in Fig. 3. However, the film formed at 328 C exhibited lower bandgap energies than those formed at 473
and 685 C. A similar phenomenon was also observed
by Mardare et al. [8]. They formed the TiO2 film on
quartz substrate using a DC sputtering technique and
investigated an influence of heat treatment. The film
heat-treated at 400 C displayed lower bandgap energies than that heat-treated at 600 C. They reported that
this phenomenon was cause by the formation of rutile
phase at lower temperatures. However, in this study, we
did not observe any rutile pahse at lower temperatures
as shown in Fig. 3. The more research about this will
be performed in near future.

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.

film, undergone annealed process at 500 C, exhibited


anatase TiO2 , indicating that Ti3+ is fully oxidized to
Ti4+ due to air exposure during reaction in solution or
due to post heat treatment. TG/DTA results for as-dried
powder at room temperature shows that the film heattreated at 990 C forms a mixture of anatase and rutile
phase through three stages: (1) the removal of physically adsorbed water (2) the decomposition of peroxo
group (3) amorphous-anatase or anatase-rutile phase
transformation. The crystallite size increases with annealing temperatures, while bandgap energies decrease
from 3.72 eV at room temperature to 3.17 eV at 990 C.
This fact is attributed to the quantum size effect and formation of rutile phase which has lower bandgap energy
than anatase.
Acknowledgment
This work was supported by grant No. R12-2002004-02-001 from the Center for Advanced Net Shape

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.
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