J Mater Sci: Mater Electron
DOI 10.1007/s10854-016-4985-4
Characterization of titania thin films grown by dip-coating
technique
Davoud Dastan1 • Seyedeh Leila Panahi1 • Nandu B. Chaure1
Received: 29 January 2016 / Accepted: 12 May 2016
Ó Springer Science+Business Media New York 2016
Abstract A dip-coating technique was employed to pre-
pare anatase phase of titania thin films. Fluorine doped tin
oxide substrates were used to prepare titania thin films. The
samples were annealed at 550 °C for 18 h. X-ray diffrac-
tion results revealed the amorphous and anatase phases of
TiO2 for as-synthesized and annealed samples, respec-
tively. The crystallite size of anatase TiO2 thin films was
almost 25 nm for annealed samples. UV–visible confirmed
the energy band gap 3.86 and 3.64 eV for as-prepared and
calcinated titania thin films. The reduction in the energy
band gap could be due to the change in crystallization and
agglomeration of small grains after calcination. The mor-
phology of the prepared films was investigated by field
emission scanning electron microscopy which demon-
strated the agglomeration of spherical particles of TiO2
with average particle size of about 30 nm. The molecular
properties (chemical bonding) of the samples were inves-
tigated by means of Fourier Transform Infrared (FTIR)
spectroscopy. FTIR analysis exhibited the formation of
titania, functional group OH, hydroxyl stretching vibrations
of the C–OH groups, bending vibration mode of H–O–H,
alkyl C–H stretch, stretching band of Ti–OH, CN asym-
metric band stretching, and C=O saturated aldehyde.
1 Introduction
Titanium dioxide (TiO2) is an excellent n-type semicon-
ductor which has been vastly studied owing to its potential
applications in areas such as biotechnology, food and
& Davoud Dastan
d.dastan61@yahoo.com
1
Department of Physics, Savitribai Phule Pune University,
Pune 411007, India
agriculture, medicine, aerospace, energy and environment,
etc. It also has an excellent physical, optical, and chemical
characteristics. Titania has large band gap, high thermal
and chemical stability, high transmittance in the visible
spectral range, high dielectric constant, and can be easily
doped with active ions [1–9].
TiO2 has different applications in optical devices,
antireflective coating, air and water purification, sensors,
solar cells, field effect transistors, and photovoltaic devices.
Moreover, nanocrystalline titania has large surface-to-
volume ratio which allow efficient gas adsorption and hence
it can be used as energy storage material for instance, it is
widely used for the fabrication of batteries and solar cells [6,
10, 11]. The amorphous and anatase phases of titania are
normally observed at temperatures lower than 300 °C and
the range from 350 to 700 °C, respectively. Anatase phase
has excellent chemical and physical properties for air and
water purification [3, 10–15].
Different techniques have been reported for the depo-
sition of TiO2 thin films such as spin coating, dip-coating,
electron beam evaporation, pulsed laser deposition, chem-
ical vapour deposition, etc. We have used dip-coating
technique for the preparation of titania thin films, because
it is one of the low-cost and easy processing methods.
Furthermore, dip-coating route has pros such as repro-
ducibility, nonhazardous, and well suitable for large area
deposition at relatively low temperatures [16, 17]. It also
provides a high degree of crystalinity, better purity and
homogeneity at ambient conditions [16–18]. It is known
that the structure and morphological features of titanium
dioxide films are significantly influenced by the experi-
mental conditions.
The features such as shape, size, crystalline form, pho-
tocatalytic activity, and some relevant properties of tita-
nium dioxide particles and thin films can be controlled by
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changing the reaction temperature and time, the pH value,
and the ratio of reactants [16, 17]. In this study, the main
aim was to prepare titania thin films on Fluorine doped tin
oxide (FTO) substrates using dip-coating technique at room
temperature and investigate their structural, optical,
molecular, and morphological properties before and after
calcination at 550 °C.
2 Experimental details
2.1 Materials
Titanium isopropoxide (TIP, C12H28O4Ti), Oley amine
(OM, C18H37N), Absolute ethanol, C2H5OH, and Acetone,
C3H6O were used for the preparation of titania thin films.
These materials were purchased from Sigma-Aldrich and
used as received.
2.2 Preparation of titania thin films using
dip-coating method
the XRD pattern of annealed sample demonstrates several
peaks at about 25.27, 37.81, 48.11, 53.93, 55.12, 62.68,
68.84, 70.34, and 75.20°, ascribed to (101), (004), (200),
(105), (211), (204), (116), (220), and (215) Miller planes
accordingly, which are attributed to the crystalline struc-
ture of the pure anatase phase of TiO2 thin films (Fig. 1b)
[19–28]. It is conspicuous that the amorphous nature of
pristine sample has been fully transformed into anatase
phase after calcination at 550 °C. The anatase crystallite
size was evaluated using the following expression [29, 30]:
D ¼ Kk=bCosh ð1Þ
where, D is the crystallite size, b is the full width at half-
maximum height (FWHM), and h is the Bragg diffraction
angle (°), k is the wavelength of the X-ray radiation (Cu
Ka = 0.15 nm), and K is the Scherrer constant (0.9). The
average crystallite size calculated for anatase titania using
the above expression was almost 25 nm. The crystallite
size normally increases when the annealing temperature
increases due to the aggregation and recrystallization of
TiO2 after heat treatment [3].

Dip coating technique was used to prepare titanium dioxide

thin films. Prior to incremental addition of titanium iso-
propoxide (TIP), oley amine (OM) was added dropwise to
absolute ethanol and the solution was under moderate
stirring for 1 h at ambient condition. These chemicals were (b)
used with molar ratio 0.2:9:1 for OM/ethanol/TIP [3]. FTO
substrates were washed in acetone, methanol, and double
distilled water prior to the deposition of TiO2. The sub-
strates then dipped into the solution. The deposited TiO2
layers were dried at room temperature and treated to post
annealing at 550 °C for 18 h [4, 5]. X-Ray Diffraction
(XRD, Advanced Brucker Diffractometer) was used to
identify the phase of pristine and annealed titania thin
films. The optical and molecular features of TiO2 speci-
mens were investigated by UV Visible (Jasco UV–vis.
spectrophotometer), and Fourier Transform Infrared (Jasco
FTIR spectrometer). The morphological properties of the (a)
prepared samples were investigated by field emission
scanning electron microscopy (FESEM, Make-FEI, Model-
NOVA NANOSEM-450).

3 Results and discussion

3.1 Structural properties

The structural properties of titania thin films were studied

by X-ray Diffraction (XRD). Figure 1a,b demonstrates the
XRD patterns of as-deposited and calcinated at 550 °C
TiO2 thin films. Figure 1a depicts the XRD pattern of as- Fig. 1 XRD patterns for a as-deposited and b calcinated at 550 °C
deposited titania thin film with amorphous nature, whereas TiO2 thin films

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J Mater Sci: Mater Electron
3.2 Optical properties
Figure 2 shows absorption and transmission spectra of
pristine and calcinated titania thin films at ambient condi-
tion. The direct transition of electrons from the valance
band to the conduction band is used for evaluating the
energy band gap (Eg) of TiO2 thin films. The absorption
edge showed a red-shift. It was nearly 341 and 321 nm
corresponding to energy band gap, 3.86 and 3.64 eV, for
as-deposited and annealed samples, respectively
(Fig. 2a,b). The as-prepared and annealed specimens
exhibited almost 70 % transmittance as shown in the
Fig. 2c,d. As expected the energy band gap and transmit-
tance decrease upon heat treatment. The former is likely
due to the agglomeration of particles on the surface or
phase transformation from amorphous to anatase and the
later is due to the increase in surface scattering owing to
the surface roughness [3, 27, 31]. These information
regarding the optical characteristics, the energy band gap
and transmittance, are particularly significant, for instance,
a reduction in the band gap and high transparency are
fruitful for the applications such as photocatalytic and
optoelectronic devices, respectively [3, 19, 27, 31]. The
(c)
(d)
(a)
(b)
Fig. 2 Absorption and transmittance spectra of (a, c) pristine and (b,
d) annealed at 550 °C TiO2 thin films
absorption coefficients (a) of the samples were calculated
using the following formula:
   
1 1
a¼ ln ð2Þ
t T
where T is the maximum of transmission spectra in the
visible region and t is the thickness of the film. The esti-
mated values of a for the as-deposited and calcinated
specimens were 95 9 106 and 93 9 106 m-1 which con-
spicuously demonstrated a decrease after post-heat treat-
ment. This phenomenon can be related to decrease in the
thickness and transmittance upon calcination and
improvement in the crystallinity [10–15].
3.3 Molecular study
Fourier transform infrared (FTIR) spectroscopy was used
to study the molecular properties of as-deposited and
annealed TiO2 films. Figure 3a,b shows the FTIR spectra
of as-prepared and annealed TiO2 thin films in the range of
600–3800 cm-1 at ambient conditions, respectively. An
asymmetrical stretching vibration at almost 3440 cm-1 is
ascribed to the stretching vibration mode of hydroxyl group
whose intensity reduces upon increase in the annealing
(b)
(a)
Fig. 3 Fourier transforms infrared (FTIR’s) spectroscopy of a as-
prepared and b calcinated at 550 °C TiO2 thin films
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Fig. 4 Field Emission Scanning Electron Microscopy (FESEM)
image of a pristine and b annealed at 550 °C titania thin films
temperature. This band is originated from the presence of
water molecules absorbed in air [32–42]. The entity of
methylene and methyl groups were demonstrated with
vibrations bands at 2928 and 2856 cm-1 [38, 40, 41].
The lattice vibration of TiO2 is demonstrated with IR
bands below 1000 cm-1 [37]. The FTIR peak centred at
1625 cm-1 is related to the bending vibrations of C=O
(ketone carbonyl) group which shows lower intensity after
heat treatment at 550 °C [26, 38, 39]. The medium
absorption with a minima at 1440 cm-1 is related to the
bending vibrations of C=C [37, 38]. The intense and
symmetric band located at 2350 cm-1 is ascribed to nitrile
group (CN) band. The above peaks elucidated the devel-
opment of TiO2 thin films.
3.4 Electron microscopy
Field emission scanning electron microscopy (FESEM)
images and energy-dispersive X-ray spectroscopy (EDS)
were used to evaluate the surface morphology and chemi-
cal composition of as-prepared and calcinated titania thin
films. The factors such as composites, calcination
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J Mater Sci: Mater Electron
Fig. 5 EDS patterns of a pristine and b calcinated at 550 °C TiO2
thin films
temperature, and preparation techniques have the remark-
able effects on the morphology of material [4]. The
FESEM images demonstrated almost spherical particles.
Figure 4a,b depicts the FESEM images of as-deposited and
annealed titania thin films. The length of shorter and longer
axis in FESEM images was considered to evaluate the
mean size of the particles. As can be seen, the size of as-
deposited particles was in the range of 20–30 nm (Fig. 4a)
while the size of calcinated particles was approximately
30–40 nm, respectively (Fig. 4b).
Therefore, annealed films showed more agglomeration
and quite larger particle size compared to as-deposited
films because of the change in the crystal structures after
calcination. On the other hand, the particle size increases
upon calcination due to decrease in the grain boundaries
and more aggregates are found for the annealed sample
compared to the pristine sample where uniform particles
are distributed. The small particle size is useful for appli-
cations such as photocatalysis activity and transparent
optical coating [20, 23, 42]. Figure 5a, b delineates the
energy dispersive X-ray spectroscopy (EDS) of pristine and
calcinated at 550 °C titania thin films. EDS was used to
confirm the presence of chemical elements such as titanium
and oxygen into the samples. Titanium and oxygen were
present in all specimens [21, 28]. The atomic percent of
J Mater Sci: Mater Electron
Table 1 EDS results for as-prepared and annealed titania thin films
Sample conditions Elements Atomic %
Pristine Ti 33.2
O 66.8
Annealed at 550 °C Ti 31.3
O 68.7
titanium and oxygen for as-prepared and annealed samples
are given in Table 1.
4 Conclusions
Titania thin films were successfully prepared using dip
coating technique and the effect of post heat treatment on
their structural, optical, morphological, and molecular
properties was investigated. The developments of amor-
phous nature and anatase phase were conspicuous for as-
deposited and annealed at 550 °C titania thin films in the
XRD patterns. Molecular study and energy-dispersive
X-ray diffraction demonstrated the deposition of titania on
FTO substrates. The results of morphological study showed
the improvement in the particle size and agglomeration of
particles after heat treatment and the elemental analysis
confirmed the presence of titanium and oxygen for all
specimens. The absorption edge was red shifted after heat
treatment and the band gaps and transmittance spectra were
reduced due to increase in the particle size, phase trans-
formation from amorphous to anatase, and the increase in
surface scattering owing to the surface roughness. Forma-
tion of titania and presence of chemical bonding such as
C=O, C=C, O–H, etc. were obvious in FTIR study. Overall,
calcination has influenced the structural, surface morphol-
ogy and optical properties of TiO2 thin films.
Acknowledgments Authors would like to thank the financial support
received from UGC under the Grant No. F. 19-1/2013(SA-I) at New
Delhi.
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