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J Sol-Gel Sci Technol (2011) 58:269276

DOI 10.1007/s10971-010-2387-2

ORIGINAL PAPER

Bandgap modification of TiO2 solgel films by Fe and Ni doping


Davinder Singh Nafa Singh Sunil Dutta Sharma
Chander Kant C. P. Sharma R. R. Pandey
K. K. Saini

Received: 24 September 2010 / Accepted: 16 December 2010 / Published online: 29 December 2010
Springer Science+Business Media, LLC 2010

Abstract Nickle and iron doped TiO2 thin films were


prepared on glass substrates by solgel dip coating process.
Indirect and direct optical energy gaps were calculated with
the incorporation of different concentrations of both the
ions. Indirect bandgap was found to be a strong function of
the dopant concentration, whereas direct energy gap has
negligible dependence on the nature of dopant and its
concentration. Direct energy gap has always been found to
retain a value higher than the indirect energy gap. Variation
of observed energy gap properties shows a trend similar to
that reported on the basis of numerical calculations or the
samples obtained by other techniques. Increase in refractive index and corresponding density of the film sample
does not support the change in turn over frequency. The
influence of crystalline phase change is also ruled out by
XRD investigations. It is concluded that red shift of band
edge absorption takes place by incorporation of dopant and
solgel dip coating technique offers an effective low cost
route to the production of these coatings.
Keywords

Solgel  Titanium oxide  Anatase  Bandgap

D. Singh  S. D. Sharma  C. Kant  C. P. Sharma 


R. R. Pandey  K. K. Saini (&)
National Physical Laboratory, Dr K. S. Krishnan Road, New
Delhi 110012, India
e-mail: krishanksaini@gmail.com
N. Singh
Department of Physics, Kurukshetra University, Kurukshetra,
India

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

report we presenting our studies on the change in direct and


indirect bandgap energies for the anatase phase of TiO2
films fabricated on glass substrates by solgel dip coating
process.

J Sol-Gel Sci Technol (2011) 58:269276

AR grade extra-pure chemicals from SigmaAldrich


were used for all preparations and all the chemicals were
used as procured.
2.3 Characterization

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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Hardness of the deposited films was tested by scotch tape


test and rubbing with cotton cloth using detergents. XRD
spectra of the annealed samples was recorded with SIMMON D500 X-ray diffractometer which uses monochro.
matized Cu Ka radiations with wavelength k = 1.541 A
Transmission and absorption spectra from 300 to 800 nm
was taken on SHIMADZU UV-3101 PC UVVis spectrophotometer and PL spectra on Perkin Elmer LS55
model.

3 Results and discussion


3.1 Film hardness
All the films, doped and undoped, were highly stable and
scratch resistant under investigations by scotch tape test
and mechanical rubbing with cotton cloth using detergents.
They were also found to be stable under harsh lab environments (containing vapors of different gases, acid fumes
etc.) and open natural environments (under Sun) kept
continuously for 6 months. Not even a single scratch or pin
hole was developed in the film and they again passed
scotch tape test after this treatment.
3.2 Crystalline structure
XRD spectra of all the doped and undoped samples were
recorded in the 2h range from 20 to 80. XRD diffraction
peaks were observed at mean 2h values, 25.4, 38.6, 48.2,
54.1, 55.2, 62.7, 68.8, and 76.2 which were assigned
hkl values as (101), (112), (200), (105), (211), (204), (116)
and (215) of the titanium oxide anatase phase. Minor shifts
in the peak positions and widening of peaks is observed in
the diffraction spectra of doped samples but they can be
conveniently assigned to the anatase phase of TiO2 confirming the formation of this phase in all the doped and
undoped samples. These shifts are attributed to the presence of strain and reduced particle size in the samples
caused by doping. A typical XRD spectrum is shown in
Fig. 1.
3.3 Photoluminescence
The Photoluminescence (PL) spectra of doped and undoped
films samples excited at 315 nm (*3.8 eV) are shown in
Fig. 2.

J Sol-Gel Sci Technol (2011) 58:269276

271

Fig. 1 Typical XRD pattern for


doped and undoped TiO2
sample

Pure TiO2 film

1400000

2 Mol% Fe/TiO2 film

1200000

10 Mol% Fe/TiO2 film

429

6 Mol% Fe/TiO2 film

1000000

441
800000

469

600000

640

531

Intensity (a.u)

1600000

400000
200000
0
400

450

500

550

600

650

Wavelength (nm)

A broad emission spectra with well resolved peaks/


shoulders at 429, 441, 469, 531 & 640 nm has been
observed in the PL spectra of Fe-doped and undoped
samples. There is blue emission in all the samples. The
strong blue emission at 430 nm or lower wavelength is
assigned to band gap luminescence. The peaks at 428 &
439 nm are strong whereas the other three peaks in the
visible range at 469, 531 & 640 nm are weak. In case of
Ni-doped samples, PL peaks are observed at 551, 595 and
640 nm. This shows two peaks at 551 & 595 nm are
generated while peaks at 428, 439 and 531 nm are wiped
out as a result of Nidoping. The high energy peaks can
be assigned to the band edge luminescence of the TiO2
particles, where low energy peaks are induced by the
presence of oxygen vacancies [16, 17]. The change in
recombination processes as a result of doping is evident
from photoluminescence studies of the samples.

2400000
2200000
2000000

Pure TiO2 film

1800000

4 mol% Ni/TiO2 film


8 mol% Ni/TiO2 film

1600000

10 mol% Ni/TiO2 film

595

1200000
1000000

640

1400000

551

Intensity

3.4 UVVis transmittance & absorption studies

800000

200000

469

429

400000

441

600000

531

0
400

450

500

550

600

650

Wavelength (nm)

Fig. 2 Photoluminescence spectra of pure Fe and Ni doped TiO2


films

Figure 3 shows the transmittance spectra of Fe and Ni


doped sol gel deposited TiO2 films of thickness 140 nm.
Three observations are there from the absorption spectra of
these samples (1) the average absorption in the visible
range decreases by *10%, in the doped films which
increases with the dopant concentration and (2) the onset of
band edge absorption shifts towards longer wavelengths
and (3) the absorption curve becomes less steeper by
incorporation of dopants into the sample. The 50%
absorption is observed at 328, 343, 353, 355, 363 and
373 nm for 0, 2, 4, 6, 8 & 10 mol % Fe doped samples
while for Ni doped samples the respective values are 328,
336, 359, 364 & 350 nm.

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272

J Sol-Gel Sci Technol (2011) 58:269276

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

2 mol % Nidoped TiO 2


4 mol % Nidoped TiO 2
6 mol % Nidoped TiO 2
8 mol % Nidoped TiO 2
10 mol % Nidoped TiO 2

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)

Fig. 3 Transmittance of pure Fe and Ni doped TiO2 films


Pure TiO2
2 mol% Fe/TiO2
4 mol% Fe/TiO2
6 mol% Fe/TiO2
8 mol% Fe/TiO2
10 mol% Fe/TiO2

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)

Fig. 4 Absorption spectra of Fe and Ni doped TiO2 films

Figure 4 shows the UVVis absorption spectra over the


wavelength range of 300460 nm for undoped Fe and Ni
doped TiO2 films. A red shift of the absorption edge has
been noticed in the absorption spectra, with increase in
dopant concentration. We have calculated indirect and
direct bandgap values for the doped sampled from the
absorption data as explained below.
3.5 Calculation of band gap

where B is a constant and p is an index that characterizes


the optical absorption process and is theoretically equal to
1/2, 2, 3/2 or 3 for direct allowed, indirect allowed, direct
forbidden and indirect forbidden transitions, respectively.
Best fit in optical absorption data obtained from many
oxide films is achieved when p = 2.
The absorption coefficient (a) of undoped and doped
films was calculated from the transmittance by using the
following formula [19]
a d1 Log 1=T

Both direct and indirect bandgaps in the Fe and Ni doped


TiO2 film samples were calculated by using Taucs equation [18]

 
a B  hm  Eg p hm
1

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Values of optical band gap have been calculated using


the well-known Taucs equation by plotting (ahm)1/2 versus
hm and extrapolating the linear portion to (ahm)1/2 = 0. The
absorption coefficient (a) was calculated from (a = 4pk/k),

J Sol-Gel Sci Technol (2011) 58:269276

273

where k is absorption coefficient. The direct optical band


gap energy was determined from the slope of (ahm2 vs. hm)
graph by linear extrapolation towards zero absorption; the
indirect band gap was evaluated from the linear
extrapolation of (ahm)1/2 versus hm graph.
Calculations of indirect and direct band gap values for
different concentrations of Fe and Ni doping are shown in
Figs. 5 and 6 respectively. Calculated numerical values for
the band gap energies are listed in Tables 1 and 2 for different concentrations of the two dopants. The indirect
bandgap was found to decrease with increase in dopant
concentration while direct bandgap increases with the
incorporation of both the cations into the solgel TiO2 films.

4.00E+014

2 Mol% Fe/TiO2 film


4 Mol% Fe/TiO2 film
6 Mol% Fe/TiO2 film
8 Mol% Fe/TiO2 film
10 Mol% Fe/TiO2 film

3.50E+014
3.00E+014

2.00E+014

2 Mol% Fe/TiO 2 film


4 Mol% Fe/TiO 2 film
6 Mol% Fe/TiO 2 film
8 Mol% Fe/TiO 2 film
10 Mol% Fe/TiO 2 film

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

We have calculated the values of refractive index of


undoped & doped (iron and nickel) TiO2 thin film samples
from reflectance-wavelength measurement and curve fitting
program (filmetrics F-20) white light spectrophotometry in
the wavelength range 4001,100 nm. An increase in the
value of refractive index from 1.80 to *1.95 was observed
with increase in Fe doping in the sample up to 6-mol % and
the corresponding increase in the value of refractive index
for Ni doped samples was from 1.70 to 1.94. Refractive
index of the samples with dopant concentration more than
6 mol % remained constant at the highest value achieved
for that dopant. These results are shown in Figs. 7a and 8a.

(h )

(h)

3.6 Refractive index of pure, Fe and Ni doped TiO2 films

2.00E+014
h (eV)

0.00E+000
2.0

2.5

3.0

3.5

Table 1 Direct and indirect band gap energies of Fe doped TiO2


films
Fe concentration in TiO2 sol (mol %) 0

We have calculated density of our film samples from the


refractive index data by using the relation by Otterman
et al. [20].


  2


P qf =qb n2f  1 n2f 2
nb 2 n2b  1

10

3.50 3.76 3.63 3.62 3.70

Indirect band gap energy in (eV)

3.30 3.12 3.14 2.8

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

Figures 7b and 8b shows the variation of packing density


of Fe: TiO2 & Ni:TiO2 films.
8000

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

Direct band gap energy in (eV)

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

3.7 Density of the film

Fig. 5 (ahm)1/2 versus hm plot


for pure Fe and Ni doped TiO2
thin films

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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J Sol-Gel Sci Technol (2011) 58:269276

structure of the lower part of conduction band and upper


part of the valence band. As per the above calculations; the
lower part of the TiO2 conduction band arises from the 3d
orbital of titanium and valence band from the 2p orbitals of
oxygen atom. In case of doped samples; these studies have
further revealed that for Fe-doping the p antibonding of Fe
eg and O pp states generates localized levels at 0.2 eV
above the top of VB, which is occupied by 4 electrons and
Fe eg is split into dz2 and dx2 y2 orbitals in the band gap
while for Ni-doping, p antibonding of Ni eg and O pp states
are delocalized and appears within VB. The Ni eg states
from the dz2 and dx2 y2 orbitals are situated in the bandgap.
The electron densities around the dopant are large in the
VB and small in the CB as compared to undoped TiO2.
Consequently metal-O interaction strengthens and metal
metal interaction becomes weak as a result of 3d metal
doping. This picture is illustrated diagrammatically in
Fig. 9 for the undoped and doped samples.
A red shift in the bandgap absorption (Fig. 3) of our Fe
and Ni samples is in accordance with the above theoretical
calculations. The large red shift in Fe doped samples is due
to the charge transfer transitions between the d electrons of
dopant and CB, as Fe doping results in localized energy
levels just above the valence band. Density of these energy
levels increases with increased doping. In contrast the Ni
doping results in delocalized electrons in the valence band,

Table 2 Direct and indirect band gap energies of Ni doped TiO2


films
Ni con in the TiO2 sol (mol %)

10

Direct band gap direct band gap


energy in (eV)

3.50

3.7

3.77

3.48

3.68

Indirect band gap indirect band


gap energy in (eV)

3.30

3.06

3.04

2.7

2.9

result of interactions of Ti 3d and O 2p orbitals. Theoretical


calculations [21] has shown that Ti 3d orbital is split into
two parts, the t2g and eg states, the CB is divided into upper
and lower parts. The VB and upper CB are composed of O
p and Ti eg states, while the lower CB consists of O p and
Ti t2g states. VB can be decomposed into three parts: r
bonding of O pr and Ti eg in the lower energy region; the p
bonding of the O pp and Ti eg states in the middle energy
region; and the O pp states in the higher energy region. The
bottom of the lower CB consisting of the Ti dxy orbital
contributes to the metalmetal interactions due to the r
bonding of the Ti t2gTi t2g states. At the top of the lower
CB, the rest of the Ti t2g states are antibonding with the O
pp states. The upper CB consists of the r anti-bonding
between the O pr and Ti eg states. The properties of a
material which are related to electronic excitations across
the bandgap are decided primarily by the electronic

(a) 1.96
1.94

(b)

1.92

Packing density

Refractive index

Fig. 7 a Refractive index and


b packing density of Fe doped
TiO2 films

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

Concentration of iron (mol %)

2.40

(b) 0.96

2.35

0.94

2.30

0.92

Packing density

(a)

Refractive index

Fig. 8 a Refractive index and


b packing density of Ni doped
TiO2 films

10

Iron concentration (mol %)

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

J Sol-Gel Sci Technol (2011) 58:269276

275

Fig. 9 Energy band diagrams


for undoped and doped TiO2
sample

thus significantly contributing to the formation of the


valence band with p and 3d electrons, which probably
causes a small shrinkage of bandgap in Ni doped samples.
Our bandgap calculations (Fig. 5, Table 1) exhibited a
change in bandgap from 3.30 to 2.73 eV in Fe doped and
from 3.3 to 2.9 eV in Ni doped samples. Similar observation of decrease in optical band edge has also been reported
by Li et al. in Nd doped TiO2 samples [22]. These findings
are opposite to the numerical calculations of Nishikawa
et al. [23]. Reason for this behavior is attributed to the fact
that these authors have assumed nickel in Ni3? state in
their numerical calculations whereas XPS studies of Marshal et al. [24] shows that nickel exists partially in Ni2?
state as well in the solgel derived TiO2 films. Yen et al.
[25] have observed a similar large change in optical
bandgap energy of TiO2 film derived by solgel technique
in which post doping is achieved by implanting Fe ions into
the TiO2 matrix at 20 keV. However the present technique
offers an easy and more effective way to obtain uniformly
doped films with the desired concentration of cation for
different applications. Further the direct energy bandgap
(Fig. 6, Table 2) is larger than the indirect energy gap in all
the samples and no significant change in its value is
observed by incorporation of Fe or Ni ions. Therefore we
do not expect any observable change in properties due to
the small change in direct bandgap energy of the sample.
The change in various properties of TiO2 films by Fe or
Ni doping is, therefore, due to two reasons (1) ability to
absorb lower energy photons to generate more electron
hole pairs. This process is assisted by the introduction of
additional energy states, by the dopant ions below the
conduction band and/or above the valence band. (2)
Reduction in recombination loss of photo-generated electronhole pairs as is evident by the reduction in various PL
peak intensities as a result of doping (Fig. 2).
It is not advisable to expect the change in observed
properties of these samples due to the increase in turn over
frequency on lines of Co3O4 catalysis [26] as the density of
the samples increase as result of doping (Fig. 8). A significant change in photocatalytic activity of Co3O4 has
been reported by change in the crystallite size from
micrometer to nanometer range in silicon oxide matrix.

Any contribution to the observed properties due to the final


crystalline phase formed is also ruled out due to the
observation of same crystalline phase in the doped and
undoped sample; however effects due to the presence of
strain need to be investigated.

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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