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CHAPTER 3
PREPARATION AND CHARACTERIZATION OF TiO2
THIN FILMS

3.1

INTRODUCTION
Nanocrystalline TiO2 thin films have been prepared by different

researchers using various techniques, such as evaporation (Toshihiro Miyata


et al 2006), spray pyrolysis (Okuya et al 2004), chemical vapour deposition
(Giovanni et al 1994), sputtering (Hossain et al 2008), laser ablation (Nicolas
Martin et al 1997) and sol-gel method (Verma et al 2005, Sabataityte
et al 2006, Guo et al 2005, Harizanov et al 2000, Yu et al 2000). In the
present study nanocrystalline TiO2 thin films have been prepared by sol-gel
dip coating technique. Dip coating technique has many advantages over other
techniques. This technique is simple and the deposition can be carried out at
room temperature. This method can be easily used for large area deposition at
low cost and the thickness of the deposited layer can be readily controlled by
varying the length of the deposition time.
In the present study TiO2 thin films have been prepared using
titanium tetra isopropoxide and isopropanol by the simple solgel dip coating
method at room temperature. The oxide network of TiO2 is formed by
hydrolysis and condensation of alkoxides followed by polymerization at
elevated temperatures. The ease of decreasing or increasing the chain length
of the alkyl group is being done easily by hydrolyzation of titanium
alkoxides. These reactions give polymeric species with OH or O bridges.

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The coordination of water to the metal is the first hydrolytic step, a proton on
H2O could then interact with the oxygen of an OR group through hydrogen
bonding leading to hydrolysis. The high reactivity of alkoxide water causes
instantaneous precipitation. The stability of the sol can be increased by
replacing water with acetic acid. Here acetic acid acts as a catalyst and also as
a chelating agent. Acetic acid induces the initiating process of hydrolysis
mechanism. Acetic acid is also used to modify the precursors molecular
structure (Sanchez et al 1992). Many factors such as crystallinity, particle
size, surface area, amount of solvent used and preparation method strongly
affects the properties of the prepared TiO2 thin films (Wang et al 1999,
Adachi et al 2003).
3.2

PREPARATION OF TiO2 THIN FILMS


TiO2 thin films with anatase phase have been prepared using

titanium tetra isopropoxide and isopropanol by the simple solgel dip coating
method at room temperature. An attempt has been made to control the
hydrolysis/condensation reaction in the solgel of TiO2 by using acetic acid.
The properties of TiO2 films are not only influenced by the deposition
technique but also by the post-annealing treatment. The solution was prepared
by mixing 1.5ml of titanium tetra isopropoxide (Alfa Aaser 99.9%) with 15ml
of isoproponal (Aldrich 99.9%) at room temperature and stirred for half an
hour. To this solution 0.365ml of glacial acetic acid was added drop wise and
stirred vigorously for 2 hours to obtain a homogeneous mixture of TiO2 sol.
The pH of the solution is 5. Using the prepared solution thin films of TiO2 were
obtained on ITO glass plates by dip coating method. The ITO glass plates were
ultrasonically cleaned using acetone, ethanol and de-ionized water. It should be
noted that cleaning of the substrate is important for proper adhesion of the films.
TiO2 thin films have been coated on ITO glass plates and heated at 80C for 10
minutes and then allowed to cool to room temperature.

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The dip coating, heating and cooling process was repeated five
times in order to get thicker films. The thickness of the films has been
determined using surface profilometer and was in the range of 0.8 0.83 m.
The heating of the film after each deposition in air is carried out to enhance
the inorganic polymerization and stabilize the formed mesophases. The films
were then dried at room temperature for 2 hrs and then annealed in air. The
films have been annealed at 400C, 450C and 500C for 1 hr using a heating
rate of 2C/min. TiO2 thin films were uniform and homogeneous. The flow
chart showing the procedure used for preparing TiO2 thin film is shown in
Figure 3.1.
Titanium isopropoxide

Isopropanol

Stirring for
30 minutes

Adding acetic acid

Stirring for 2 hours

TiO2 sol

Dip coating

Annealing at different
temperature

TiO2 thin
films

Figure 3.1 Flow chart depicting the preparation of the TiO2 thin films

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3.3

STRUCTURAL PROPERTIES
The structural properties of the prepared TiO2 films have been

studied using X-ray diffraction method, scanning electron microscope, atomic


force microscopy and high resolution transmission electron microscope. The
composition of the films have been analyzed using energy dispersive X-ray
analysis. During the formation process of TiO2, mono TiOH is formed
during the hydrolysis reaction and TiOH aggregation results in the formation
of crystalline nuclei and the primary particle size depends on the aggregation
degree. Finally the particles in the film are oxidized and turned into oxide
form during calcination at higher temperature and this promotes the formation
of TiOTi anatase bonds.
The X-ray diffraction studies revealed that the as deposited films
are amorphous in nature. The prepared TiO2 films have been annealed at
400C, 450C and 500C. The X-ray diffraction pattern of the TiO2 films
annealed at different temperatures is shown in figure 3.2. The diffraction
pattern shows a peak at 25.31 degrees which corresponds to the (101) plane of
the anatase phase of TiO2. The presence of very small peaks in the 400C
annealed film shows that nucleation of grain has started. The presence of
sharp peaks in the 450C and 500C annealed samples shows that the grains
have started to grow on annealing. The observed peaks corresponds to (1 0 1),
(0 0 4), (2 0 0), (1 0 5), (2 1 1) and (2 0 4) planes. No peaks corresponding to
the rutile or brookite phase has been observed in the X-ray diffraction pattern.
The diffraction pattern displays the coexistence of both amorphous and
crystalline TiO2 regions and this is observed by simultaneous presence of the
broad hump in the low 2

region demonstrating short range order and

amorphicity. It should be noted that the heat treatment temperature above


400C makes the intensity of the peak to increase, with reduction in full width
at half maximum (FWHM). This is due to the transformation of TiO2 from
amorphous to crystalline nature on heat treatment.

(204)

(105)
(211)

(200)

(004)

Intensity (a.u.)

(101)

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500 C
450 C
400 C
10

20

30

40

Figure 3.2

50

60

70

80

(degrees)

X-ray diffraction pattern of TiO2 thin films annealed at


different temperatures

The lattice parameter values a and c have been calculated using the
relation,
1
d2

h2

k2
a2

l2
c2

(3.1)

The lattice parameters have been calculated and were found to be


a = 3.754 and c = 9.526 and the values are in good agreement with the
standard values (JCPDS No. 21-1272, a = 3.728 and c = 9.513 ). The
crystallite size has been calculated using scherrers formula

k
cos

(3.2)

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where, D is the grain size, K is a constant taken to be 0.94,


wavelength of the x-ray radiation,

is the

is the full width at half maximum and

is

the angle of diffraction.


Table 3.1 shows the variation in grain size with annealing
temperature. Grain size is found to increase with annealing temperature.
Table 3.1 Grain size of TiO2 thin films annealed at different temperatures
Annealing

Grain

temperature (C)

Size(nm)

400

11

450

19

500

28

Figure 3.3 shows the scanning electron microscope images of TiO2


thin films annealed at 400C 450C and 500C. The films annealed at 400C
contain pores and grains of smaller size. When the annealing temperature is
raised to 450C and 500C, the grain size is found to increase. The SEM
image of the TiO2 film shows the formation of nanosized smooth grains all
over the surface with meso-sized pores in between the grains. Such type of
porous structure resulted due to the nucleation and coalescence of small
particles. The films are observed to have smooth surface morphology without
any cracks.

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(a)

(b)

(c)

Figure 3.3

SEM images of TiO2 thin films annealed at a) 400C,


b) 450C and c) 500C

Energy dispersive x-ray analysis (EDAX) pattern of TiO2 thin films


annealed at 400C, 450C and 500C are shown in Figures 3.4(a, b and c).
The origin of copper is from the copper coating on the film. The pattern
shows that the 400C annealed TiO2 film has a composition of Ti - 30.35 at %
and O - 69.65 at %. The 450C annealed film has a composition of Ti- 33.33
at % and O - 66.67 at %, and 500C annealed film has a composition of Ti35.23 at % and O - 64.77 at %. As the annealing temperature increases there
is a decrease in oxygen content and this may be due to the evaporation of
oxygen on annealing.

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Intensity (a.u)

Ti=30.35%
O =69.65%

(a)

Energy (KeV)
(b)

Intensity (a.u)

Ti=33.33%
O=66.67%

Energy (KeV)

Intensity (a.u)

(c)
Ti = 35.23% O
= 64.77%

Energy (KeV)

Figure 3.4

EDAX pattern of TiO2 thin films annealed at (a) 400C


(b) 450C (c) 500C

Figures 3.5(a, b and c) show the atomic force microscope images of


the dip-coated TiO2 thin films prepared and annealed at 400C, 450C and

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500C respectively. The image shows well-defined particle-like features with
granular topography and indicates the presence of small crystalline grains.
Because of the heat treatment, the nano crystalline phase has been formed and
this has led to the appearance of grains making the films to have higher surface
roughness. Evaluation of surface pattern was conducted by estimating the
roughness of the film (root mean square). The atomic force microscope image
shows the formation of mesoporous TiO2 films. It can be seen that the particles
are distributed homogeneously with porosity consistent with a high surface area
structure. The root mean square surface roughness of the film was found to be 19
nm, 27nm and 32nm for the TiO2 films annealed at 400C, 450C and 500C.

(a)

(b)

(c)

Figure 3.5 AFM images of TiO2 thin films annealed at a) 400C,


b) 450C and c) 500C

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High-resolution transmission electron microscopy was used to


investigate the microstructure of TiO2 nanocrystalline films. For highresolution transmission electron microscopy analysis, the TiO2 film was
peeled off from the substrate and dispersed in acetone. The solution was
sonicated for 30 minutes. The high-resolution transmission electron
microscope images of the dip coated TiO2 films annealed at 400C, 450C
and 500C are shown in Figures 3.6, 3.7 and 3.8. Figures 3.6 (a, b and c)
shows the high resolution transmission electron microscopy images of TiO2
film annealed at 400C. Figure 3.6 (a) shows the closely-packed
agglomeration of the nanoparticles in the mesoporous structure. This
accumulation of nanoparticles creates narrow channels that may serve as
electronic injection membranes. It can be seen from figure 3.6(b) that the size
of the nano particles is extremely uniform. Figure 3.6(c and d) shows lattice
fringes and the interplanar distance is measured to be 0.35 nm. Figures 3.7
and 3.8 shows the high-resolution transmission electron microscope images of
the films annealed at 450C and 500C. For films annealed at 450C and
500C the inter planar distance is measured using lattice fringes of
Figures 3.7(c) and 3.8(c) and the value is found to be 0.35 nm and 0.36 nm.
The obtained interplanar spacing values correspond to the (101) plane of
anatase phase TiO2. HRTEM images shows that there is an increase in grain
size with increase in annealing temperature.

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(a)

(b)

20 nm

10 nm
(c)

(d)
0.35nm
(101)

5 nm

2nm

Figure 3.6 HRTEM image of 400C annealed TiO2 thin film

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(b)

(a)

20 nm

10nm
(d)

(c)
(101)

5nm

0.35nm

2nm

Figure 3.7 HRTEM image of 450C annealed TiO2 thin film

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(a)

(b)

10nm

20nm
(c)

(d)
(101)

5nm

0.36nm

2nm

Figure 3.8 HRTEM image of 500C annealed TiO2 thin film


Figures 3.9 (a, b and c) shows the selected area electron diffraction
images of TiO2 nanocrysalline thin films annealed at 400C, 450C and
500C. Selected area electron diffraction pattern is used to study about the
crystal properties of a particular region. The presences of rings with discrete
spots suggest that the TiO2 nanocrystalline film is made of small particles of
uniform size. Ring patterns corresponding to planes: (1 0 1), (0 0 4), (2 0 0),
(1 0 5), (2 1 1) and (2 0 4) are consistent with the peaks observed in XRD

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patterns. The distance from centre to each ring (moving from smallest to
larger ones) is measured to be 2.810, 4.208, 5.155, 6.024 and 6.756 nm
respectively for film annealed at 400C, 2.840, 4.232, 5.154, 5.847, 6.015 and
6.752 nm respectively for film annealed at 450C and 2.717, 4.202, 4.950,
5.617, 5.992, and 6.743 nm for film annealed at 500C respectively. It is clear
from Table 3.2 that d values calculated from selected area electron diffraction
patterns of nanocrystalline TiO2 thin films are matching well with standard d
values of JCPDS data. The analysis of SAED patterns reveals the existence of
anatase phase without any secondary (brookite and rutile) or impurity phase.
(105)

(200)

(105)

(200)

(211)

(105)

(200)

(211)

(211)

(a)

(004)

Figure 3.9

(b)

(204)

(204)

(101)

(c)

(204)
(204)

(004)

(004)

(101)

(101)

Selected area electron diffraction images of TiO2 thin films


annealed at a) 400C, b) 450C and c) 500C

Table 3.2 Calculated d spacing value of different planes of TiO2 thin films
Calculated d values from TEM

400C
450C
500C
3.55
3.52
3.68
2.37
2.36
2.38
1.94
1.94
2.02
1.70
1.71
1.78
1.66
1.66
1.66
1.48
1.48
1.48

Reported d value
(JCPDS)
3.52
2.37
1.89
1.69
1.66
1.48

Planes
(hkl)
(101)
(004)
(200)
(105)
(211)
(204)

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3.4

FOURIER TRANSFORM INFRA RED SPECTROSCOPY


Fourier Transform Infrared (FTIR) spectroscopy is a promising

method for observing molecular vibrations. Figure 3.10 shows the FTIR
spectra of TiO2 thin films annealed at 400C, 450C and 500C. The thin
films annealed at 400,450 and 500C have peaks above 3500 cm-1 which
represents the OH stretching of hydrogen bonds present on the anatase TiO2
surface. A reaction with a hydroxyl anion is thought of as the initial step of
the photo oxidation of water. Since the TiO2 sol layer has relatively small
hardness and soft surface, it seems to be easy to dissociate the water or
oxygen molecules from the sol surface. The hydrate water vibration peak at
1550 cm-1 is still observed for all the three temperatures. This may be related
to water bound to TiO2 or may be due to the presence of reduced oxidant salt
species or TiO2 in a hydrate form (Lu et al 2006). The films annealed at
400C exhibits a band at 3718 cm-1 which is not observed for the films
annealed at 450C and 500C respectively, and this is due to the removal of
hydroxide group after annealing at higher temperatures. The intense band
below 1550 cm-1 is due to Ti-O-Ti vibrations. The slight shift of the band to
the lower wave numbers and sharpening of the Ti-O-Ti band on annealing
may be due to the increase in size of the nanoparticles. In addition, the surface
hydroxyl groups in TiO2 increases with the increase of annealing temperature.
There is no band centered at 1389 cm-1 which clearly shows the absence of
the C-H bond in the TiO2 films (Wang et al 2001). Also, there are no
additional bands present in the spectra corresponding to the alkoxy groups.
This reveals that the addition of acetic acid has not introduced any residual
impurities on the TiO2 surface.

Transmittance (a.u.)

50

3842
3718 3610

2715

1550

2337

400C

1735 1527
3842

1373

2924
2546

948

1735 1550

450C
956

3842
956

500C

4000

3500

3000

2500

2000

1500

Wavenumber (cm-1)

1000

Figure 3.10 FTIR spectra of TiO2 thin films annealed at 400C, 450C
and 500C
3.5

RAMAN SPECTRA
Raman spectroscopy technique is a non-destructive method capable

of elucidating the titania structural complexity as peaks from each crystalline


phase is clearly separated in frequency, and therefore the anatase and rutile
phases are easily distinguishable. Figure 3.11 shows the Raman spectra of the
nano crystalline TiO2 samples annealed at 400C, 450C and 500C. Raman
peaks originate from the vibration of molecular bonds, that is, vibrational
mode Eg, B1g and A1g peaks, which are related to different crystal planes.
According to factor group analysis, anatase has six Raman active modes (A1g
+ 2B1g + 3Eg). Ohsaka et al (1980) have reported the Raman spectra of
anatase TiO2 and have stated that six allowed modes appear at 144 cm 1 (Eg),
197 cm 1 (Eg), 399 cm

(B1g), 513 cm 1 (A1g), 519 cm 1 (B1g), and 639 cm

(Eg). The Raman spectra of the prepared nano crystalline TiO2 samples has
vibrational peaks at 143 cm 1, 197 cm 1, 396 cm 1, 519 cm

and 638 cm 1.

The absence of overlapping broad peaks show that the material is well
crystallized, with low number of imperfect sites. These peaks are

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unambiguously attributed to the anatase modification. A special attention
must be given to the Raman peaks observed at 143 cm 1, 197 cm 1, 396 cm 1,
519 cm 1, 638 cm 1which are all slightly shifted, probably due to a smaller
size of TiO2 nano crystalline particles. The peaks corresponding to the rutile
phase was not detected in the Raman spectra. This result agrees with Jorge
Medina - Valtierra et al 2006 who have observed that only the typical bands
of anatase are present in the spectra of TiO2 films annealed at temperatures
below 700C.
TiO2 nanoparticles have been frequently investigated using Raman
spectroscopy because of the unusual band broadening and shifts of Raman
bands with decreasing particle size. However, there is no general agreement
about the origin of the broadening and shifts of the Raman bands. Xu et al
(2001) have tried to explain the variation in the Raman bands with a phonon
confinement model. On the basis of the Heisenberg uncertainty principle, the
relationship between particle size and phonon position can be expressed as
follows:
x. p

/4

(3.3)

where x is the particle size, p is the phonon momentum distribution, and

is the reduced Plancks constant. As the particle size decreases, the phonon is
increasingly confined within the particle and the phonon momentum
distribution increases. This broadening of the phonon momentum leads to a
broadening of the scattered phonon momentum according to the law of
conservation of momentum. This phonon dispersion causes asymmetric
broadening and may lead to a shift of the Raman bands. From the Raman
spectra it is understood that the main spectral features of TiO2 films annealed
at different temperatures are closely similar which mean that the prepared
samples posses a certain degree of long range order of the anatase phase. The
spectra vary symmetrically with grain size. There is spectroscopic line

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broadening and merging, to line intensity decreases and there is position
shifting with decrease in annealing temperature. The full-widths at halfmaximum (FWHM) of the bands are given in Table 3.3. Comparing the three
Raman spectra, it is clear that the Raman bands shift towards higher wave
number and their intensities relatively increase as the particle size increases.
However, the band broadening is very small and is insignificant.

Intensity(a.u)

Eg

Eg

B1g

200

400

A1g

Eg
500 C
450 C
400 C
600

800

1000

Raman shift cm-1

Figure 3.11 Raman spectra of TiO2 film annealed at 400C, 450C and
500C
Table 3.3 FWHM of the peaks present in Raman spectra
Temp C

Eg

Eg

B1g

A1g

Eg

400

20

17

23

450

12

21

23

25

500

26

24

26

27

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3.6

OPTICAL STUDIES
The optical properties of TiO2 films have been studied using the

transmittance

spectra

recorded

using

UV-Vis

spectrophotometer.

Figure 3.12 shows the optical transmittance spectra of the TiO2 films
annealed at different temperatures. A significant decrease in the transmittance
below 500nm wavelength can be assigned to absorption of light caused by the
excitation of electrons from the valence band to the conduction band of
titania. It should also be noted that the transmittance of the films decreases
with increase of the heat treatment temperature. This may be due to the
formation of larger particles on the surface of TiO2 thin film, which causes
the scattering of light. The UVVis transmittance spectra shows that the
absorption edge shifts to longer wavelength with increase in heat treatment
temperature and the red-shift of absorption edge can be attributed to the
increase in grain size of TiO2 films on annealing.
Using the optical transmittance spectra, the absorption coefficient
and the band gap of TiO2 films have been determined. The absorption
coefficient was calculated using the relation, =ln (1/T)/t, where T is the
transmittance and t the thickness of the film. The absorption coefficient ( )
of the TiO2 films is of the order of 105cm-1. The band gap energy has been
calculated by plotting (

) 2 versus the photon energy (h ), and extrapolating

the linear portion of the curve to intercept the h axis. Plot of (

) 2 versus

photon energy (h ) of TiO2 films annealed at different temperatures is shown


in Figure 3.13.

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100
400 C
450 C
500 C

Transmittance (%)

80

60

40

20

500

1000

1500

2000

2500

Wavelength (nm)

Figure 3.12 Transmittance spectra of the TiO2 thin films annealed at


400C, 450C and 500C

2.00E+014

(ah )2 (eV/m)2

1.60E+014

1.20E+014

500 C
450 C

8.00E+013

450 C
4.00E+013

0.00E+000

2.5

3.0

3.5

4.0

h (eV)

Figure 3.13 Plot of (


) 2 versus (h ) of TiO2 thin films annealed at
400C, 450C and 500C

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Table 3.4 Band gap value of the TiO2 films annealed at different
temperatures
Annealing temperature
(C)
400

Band gap
(eV)
3.73

450

3.69

500

3.61

The obtained band gap values of the TiO2 film annealed at different
temperatures are given in Table 3.4. It is found that the band gap energy of
the film decreases with increase in annealing temperature. This is due to the
increase in grain size on annealing. The estimated values of band gap are in
agreement with the reported values (Boschloo et al 1997).
3.7

PHOTOLUMINESCENCE STUDIES
Figure 3.14 shows the photoluminescence spectra of the

nanocrystalline TiO2 thin films annealed at 400C, 450C and 500C. The
excitation wavelength used was 320 nm. The photoluminescence spectra of
the TiO2 thin films contain various emission features, with intensity and
position depending on the preparation conditions. The peak present at 387 nm
corresponds to the band-to-band transition due to excitation of electrons from
valence band to conduction band. The band gap calculated using this peak is
3.60eV, which corresponds to the band gap of anatase phase of TiO2 thin
films. The presence of broader photoluminescence band in the visible green
region is attributed to the recombination of photo-generated holes with the
singly ionized oxygen vacancies. There is a weak broad band in the visible
region (bluish-green and yellow-green emission). The bluish-green and

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yellow-green emissions are attributed to deep level defects in TiO2 films, such
as doubly-ionized and single-ionized interstitial Ti vacancies and oxygen
vacancies (Senthil et al 2011). The broadening of a visible band is attributed
to the porous structure of the films. The main peaks are located at about 387
and 485 nm. In the nanocrystalline regime, since the number of molecules at
the surface is more, surface defects play a vital role in determining the
luminescence characteristics. Lei et al (2001), Green et al (1997) have
reported that nano structured titania exhibit broad emission band centered at
360 550 nm at room temperature.
In general, the PL spectra of anatase TiO2 materials are attributed
to three kinds of physical origins: self-trapped excitons (Tang et al 1993,
Saraf et al 1998), oxygen vacancies (Saraf et al 1998, Serpone 1995) and surface
states (Fross et al 1993). Most of the surface states are oxygen vacancies or the
Ti4+ ions adjacent to oxygen vacancies (Redmond et al 1993, Lu 1994). The
PL of anatase TiO2 can be interpreted as due to the recombination via selftrapped excitons located or trapped on TiO6 octahedra and this originates
from the defect states present. The oxygen impurities are a kind of intrinsic
defects in TiO2 lattice and form intermediate energy levels within TiO2 band
gap introducing many recombination centres for photo induced electrons and
holes (Gratzel 1989). The Ti-OH on TiO2 surface is a kind of surface state
different from bulk defects because they can act as surface recombination
centres (Kozuka et al 2000, Li 2002). The defect states in TiO2 can be easily
understood from the following relations (David et al 1995).
TiO2

TiO2 (e- / h+) (e-CB + h+VB)

VOO+ e-CB

VO (e- trapping in shallow traps)

VO+ h+VB

VOO + h (radiative recombination)

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where VOO in the Kroger notation is an ionized oxygen vacancy level which
rapidly traps a photo-generated conduction band electron (e-CB). This
subsequently interacts with a valence band hole (h+VB ) either radiatively or
non radiatively (David et al 1995). They have reported a narrow PL peak at
3.37eV for anatase TiO2 thin films and a broad band spread over the entire
visible region for the anatase phase. The strong PL band for the anatase TiO2
is mainly due to enhanced localization of impurity and defect trapped
excitons which induce impurity levels in the energy gap of TiO2.
Mathew et al (2012) have explained the photoluminescence spectra
of the TiO2 nano particles and have reported that the luminescence is due to
the presence of defect levels caused by the oxygen vacancies.
1100

PL Intensity (arb.units)

1000
900
800
700

500C
450C

600

400C
500
400
300

350

400
450
Wavelength (nm)

500

Figure 3.14 Photoluminescence spectra of the TiO2 thin films annealed


at 400,450 and 500C

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The structural and optical properties of TiO2 films reveal that the
prepared films are uniform, homogeneous, mesoporous and are of anatase
phase. When the annealing temperature was increased the grains started
growing and at 500C the grain size was about 28nm. Since anatase TiO2
nanocrystalline films are more suitable than rutile and brookite structure for
solar cell applications the prepared TiO2 films are used for solar cell
applications.