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DOI 10.1007/s10971-010-2387-2
ORIGINAL PAPER
Received: 24 September 2010 / Accepted: 16 December 2010 / Published online: 29 December 2010
Springer Science+Business Media, LLC 2010
1 Introduction
Titanium oxide has interesting electrical and optical
properties, due to which it has found number of applications in diverse areas like photocatalytic [15], gas sensors
[68], in devices require high dielectric constant material.
Titanium oxide exists in three crystalline forms anatase,
rutile and brookite. It is anatase form of titanium oxide
which is useful for photocatalytic and gas sensor applications while rutile phase is suitable for high dielectric constant application point of view. The minimum reported
bandgap is indirect type in anatase material and direct in
the rutile phase. Various applications of the material are
sensitive to its bandgap which can be modified by doping
the material with cations or anions impurities. As a result
of doping a large change in the applied properties,
including absorption of visible photons, has been reported
[913]. Both direct as well as indirect bandgaps are
affected by the nature and concentration of the incorporated impurities, but no systematic study of this property
has appeared in the literature. Further most of the reported
studies on various properties of TiO2 films are carried out
by fabricating the films with vacuum systems such as
sputtering, e-beam evaporation etc. sub-stoichiometric
phases of the material, with poor composition control, are
evident from these techniques.
Contrary to the vacuum techniques solgel technique
offers a versatile route to obtain uniform films of TiO2 on
large area substrates and is suitable for economic production of such coatings at industrial level. Also nano-particles
of the material doped with different concentrations of
impurities can be conveniently prepared by this route using
suitable salts of the dopand ions. Complete dissolution of
the impurities in a suitable solvent ensures molecular level
mixing and hence uniform doping of the samples. In this
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270
2 Experimental
2.1 Preparation of TiO2 precursor for thin film coating
Nano particles of iron doped and undoped TiO2 have been
synthesized by solgel route, leading to zero gel and finally
annealing at 400 C for 3 h.
A 0.5 molar solution of titanium butaoxide was prepared
in isopropyl alcohol. This solution was partially hydrolyzed
by adding calculated amount of water and HNO3 as catalyst for the hydrolization reaction as reported by Sharma
et al. [14]. The mixture was stirred vigorously with the help
of magnetic stirrer, a clear transparent sol was obtained.
This sol was further used to deposit undoped and doped
titanium oxide films and also the nano-crystalline powders
of titanium in pure or doped form.
2.2 Preparation of pure TiO2, Fe and Ni doped TiO2
films
Ultra clean substrates, cleaned as per the procedure
described elsewhere [15], were used for all thin film
depositions. Films were deposited on the cleaned substrates
by dip coater designed indigenously. Substrates were dipped into the solution and allowed to settle for few minutes
so as all the vibrations are damped and then pulled out at
constant pre-decided speed. We have pulled the substrates
at 24 cms/min to achieve coated film thickness of 140 nm.
Pure TiO2 sol was used to get undoped films. To deposit Fe
or Ni doped films a stock solution of iron acetylacetonate
or nickel acetyleacetonate was prepared in isopropyl
alcohol. Calculated quantities of this stock solution were
added to the pure TiO2 sol to achieve desired dopant
concentration in the sol. Doped TiO2 films were deposited
from this sol in a similar manner as above. Film deposited
substrates were dried at 80 C for 30 min. Film deposition
and drying steps were carried out under controlled
humidity conditions (RH \ 50%) to have transparent films.
Dried films were then annealed at 500 C for 2 h in an
programmed electric furnace under atmospheric conditions
by raising the furnace temperature at the rate of 3 C/min.
To obtain nano-crystalline particles of doped or undoped
titania; the sol without or with desired concentration of
dopant was first converted to xero-gel at 80 C and then
annealed at 450 C in the furnace under conditions identical to the films.
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271
1400000
1200000
429
1000000
441
800000
469
600000
640
531
Intensity (a.u)
1600000
400000
200000
0
400
450
500
550
600
650
Wavelength (nm)
2400000
2200000
2000000
1800000
1600000
595
1200000
1000000
640
1400000
551
Intensity
800000
200000
469
429
400000
441
600000
531
0
400
450
500
550
600
650
Wavelength (nm)
123
272
1.0
80
60
Pure TiO2
2 mol % fe/TiO2
4 mol % fe/TiO2
6 mol % fe/TiO2
8 mol % fe/TiO2
10 mol % fe/TiO2
40
20
Transmittance (%)
X 100
Transmittance (%)
0.8
0.6
0.4
0.2
0.0
0
300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700
300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700
Wavelength (nm)
Wavelength (nm)
2.5
1.5
1.0
0.5
2 mol% Ni/TiO2
6 mol% Ni/TiO2
8 mol% Ni/TiO2
10 mol% Ni/TiO2
3.5
3.0
Absorbance %
Absorbance %
2.0
4.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0
300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460
300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460
Wavelength (nm)
Wavelength (nm)
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273
4.00E+014
3.50E+014
3.00E+014
2.00E+014
1.50E+014
(h )
(h )
2.50E+014
1.00E+014
0.00E+000
5.00E+013
3.5
4.0
Energy (eV)
0.00E+000
-5.00E+013
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Energy (eV)
8.00E+014
2 mol % Ni/TiO2
4 mol % Ni/TiO2
6 mol % Ni/TiO2
10 mol % Ni/TiO2
6.00E+014
4.00E+014
2.00E+014
2
(h )
(h)
2.00E+014
h (eV)
0.00E+000
2.0
2.5
3.0
3.5
10
2.73
Anantase form of titanium oxide is a wide bandgap semiconductor (EBG * 3.2 eV). Similar to other solids, the
valence band (VB) and conduction band (CB) arise as a
6000
2 mol% Fe/TiO2
4 mol% Fe/TiO2
6 mol% Fe/TiO2
8 mol% Fe/TiO2
10 mol% Fe/TiO2
6000
5000
2 mol % Ni/TiO2
4 mol % Ni/TiO2
6 mol % Ni/TiO2
8 mol % Ni/TiO2
10 mol % Ni/TiO2
4500
( h )
5000
5500
1/2
7000
1/2
4 Discussion
(h)
4.5
Fig. 6 (ahm)2 versus hm plot for pure Fe and Ni doped TiO2 thin films.
Inset shows the magnified view near the turning point
4.0
h (eV)
4000
3000
4000
3500
3000
2500
2000
2000
1500
1000
1000
500
0
0
0.0
0.5
1.0
1.5
2.0
2.5
hv (eV)
3.0
3.5
4.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
h (eV)
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274
10
3.50
3.7
3.77
3.48
3.68
3.30
3.06
3.04
2.7
2.9
(a) 1.96
1.94
(b)
1.92
Packing density
Refractive index
1.90
1.88
1.86
1.84
1.82
1.80
1.78
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
10
2.40
(b) 0.96
2.35
0.94
2.30
0.92
Packing density
(a)
Refractive index
10
2.25
2.20
2.15
2.10
2.05
0.90
0.88
0.86
0.84
0.82
0.80
2.00
0.78
2
Concentration of Ni
123
10
Concentration of Ni
10
275
5 Conclusions
Iron and nickel ion doped TiO2 film can be prepared by
solgel dip coating techniques, exhibits a large change in
the optical energy bandgap. The observed changes are
similar to that predicted by theoretical calculations and as
reported for Fe ion implanted TiO2 matrix. But in case of
nickel doping, the doped ions exists partially in the two and
three oxidation states, therefore the observed results do not
fully comply with the calculated results. Change in indirect
bandgap energy does not seem to play a significant role,
but the effect of crystallite size to increase the turn over
frequency on the lines similar to cobalt oxides, needs to be
explored further.
The present investigations shows clearly that the films of
TiO2 doped with Ni and Fe ions prepared by solgel dip
coating process are equally good as those obtained by other
techniques with respect to their light absorbing properties.
Further the solgel route gives highly stable scratch resistant films of the material in a very economical way.
Therefore this has a potential for commercial production
the films for various applications.
Acknowledgments Authors are thankful to the Director, National
Physical Laboratory, New Delhi for his keen interest and continuous
encouragement to carry out this work. One of the authors Dr. Sunil
Dutta Sharma is thankful to Department of Science and Technology
for the financial assistance. We are also thankful to Dr. A. Basu, Dr.
Shanta Chawla and Dr. D. P. Singh for their help in the characterization of these samples.
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