International Journal of Integrated Engineering (Issue on Electrical and Electronic Engineering)

Structural and Electrical Properties of TiO2 Thin

Film Derived from Sol-gel Method using
Titanium (IV) Butoxide
Isrihetty Senain1*, Nafarizal Nayan1, Hashim Saim2
1
Microelectronic and Nanotechnology – Shamsuddin Research Centre (MiNT-SRC),
Faculty of Electrical & Electronic Engineering, Universiti Tun Hussein Onn Malaysia (UTHM)
2
Faculty of Science, Arts and Heritage, Universiti Tun Hussein Onn Malaysia (UTHM)
*Corresponding email: isrihetty@gmail.com

Abstract
Fabrication of titanium dioxide (TiO2) thin film on microscope glass using sol-gel method
has been studied intensively. The starting materials were titanium (IV) butoxide, ethanol, acetic
acid, triton x-100, hydrochloric acid and deionized water. The materials were mixed together to
form the sols. Then, the heat and ageing treatment was applied to form stable sols. The sols were
then spin coated on the glass substrate to form the homogenous and transparent TiO2 thin film. The
TiO2 thin film was coated at several layers using specific conditions. To evaluate the performance
of thin film, the crystallinity of the thin film was determined by using the x-ray diffractometer
(XRD). The change on the surface morphology was observed using atomic force microscope
(AFM). The electrical property of the thin film was determined by doing the current-voltage (I-V)
analysis on the thin film. It has been successfully shown that the anatase crystalline phase was
observed when the TiO2 thin film was heated at 500°C. The roughness and the crystalline phase of
TiO2 thin film changed drastically with the growth conditions. Finally, the effect of film
preparation to the film resistivity also showed a critical aspect where we should take into account
during the preparation of TiO2 thin film.

Keywords: structural properties, electrical properties, TiO2 thin film, titanium butoxide.

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the rutile phase was formed. Furthermore, it has

1. INTRODUCTION been reported that the anatase structure formed
Titanium dioxide (TiO2) has been influences the photo catalytic activity of TiO2
investigated by many researcher because of thin film [8]. Therefore, in general the property
their numerous application in the various of TiO2 thin film is strictly depended on
industries. A transparent TiO2 thin film can be growth condition and materials.
applied for coating such as for a self-cleaning In the present research, synthesis of TiO2
glass and solar cell application. TiO2 solar cells thin film using titanium (IV) butoxide by spin
(Dye-sensitized solar cells: DSSCs) were an coating method is intensively studied. The
extensive research due to low cost, easily influence of the processes recipe to the
fabricated, environmentally benign and have structural and electrical properties is
relatively high energy conversion efficiency investigated.
[1]. Because of its numerous electrical, optical
and chemical properties, TiO2 is also used in a 2. EXPERIMENTAL
wide range of application such as catalysis,
optical coatings, gas sensors and many more. It 2.1. Substrate
has been reported that TiO2 porous film plays a
key role in the enhancement of photoelectric In this experiment the substrate used is
conversion efficiency of DSSCs. Therefore, microscope glass. The glass substrate was first
many scientists focus their researches on this treated with acetone, methanol and distilled
particular subject [2,3,4].
water in ultrasonic bath for 10 minutes each.
There are number of methods have been
Then, the substrate was blow with N2 gas for
employed to fabricate TiO2 thin films,
including reactive sputtering, chemical vapor drying purpose.
deposition, and sol–gel process. The sol-gel
technique offers many advantages over other 2.2. TiO2 solution
deposition techniques due to the use of very
simple and inexpensive equipment. Novel Using a sol-gel technique, TiO2 thin film was
morphologies can be obtained and novel prepared by mixing titanium (IV) butoxide,
physical properties may be expected depending glacial acetic acid, ethanol, deionized water and
on the structures which are not produced by the triton x-100. In order to investigate the
usual processes. This simple method has also influence of amount of solvent, the amount of
advantages to produce TiO2 thin films in a ethanol was varies for 20% and 70%. In this
relatively shorter processing time at lower technique, titanium butoxide was used as
temperatures. The rheological properties of sols precursor, glacial acetic acid as a chelating
and gels can give rise to the formation of films agent, ethanol as a solvent and deionised water
and thus considerably increase the anisotropy as a function of adding the oxygen (O2). Triton
of the material and its chemical reactivity [5]. X-100 used acts as a stabilizer to avoid
However, it is very important to study the precipitation in solution and at the same time
evolution of different physical and chemical used to increase the conductivity of films.
properties of TiO2, prepared by a suitable The hydrolysis and the polycondensation of
technique which is effective for controlled titanium alkoxides proceeds according to the
modification. N.Wetchakun et. al. claimed that following scheme:
the annealing process influence the nanosize of
TiO2 structure [6]. Fernando Gordillo Delgado Ti(OR)4 + H2O → Ti(OR)3(OH) + ROH,
et. al. also reported that the crytallinity of TiO2
thin film depend on the growth condition and Ti(OR)4 + Ti(OR)3(OH) →Ti2O(OR)6 + ROH.
the number of layer TiO2 colloidal coated [7].
C.Su et. al. then claimed that TiO2 thin film is The reaction stops with the inclusion of two
sensitive to heat treatment. The anatase phase water molecules:
was formed when at growth temperature
between 400OC to 700OC and then after 700OC Ti(OR)4 + 2H2O →TiO2 + 4ROH.

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V A
2.3. TiO2 thin film  (Ω cm)
I L
The TiO2 solution then was coated onto Where ρ is resistivity, V over I is calculated
substrate by using spin coating technique. After resistance, A is cross sectional area and L is
that, the sample was heated at 100OC. The distance between metal contacts. The thickness
process of coating and heating was repeated in of the nanostructured TiO2 thin film was
different times. The process repeated represents measured by surface profiler (Alpha Step IQ-
the number of layer of TiO2 thin film. As- KLA Tencor). Figure 1 shows the overall
prepared sample was carried to annealing experimental produce used in this research.
process at 500OC in 1 hour.

2.4. Characterization

2.4.1. X-ray diffraction (XRD) Preparation of substrate Preparation of TiO2 solution

The nanostructured TiO2 thin film was

characterized used Bruker D8 Advanced at Cleaning Substrate Thermal and ageing
room temperature. The measurement was
obtained at 2θ degree equipped with Cu Kα Coating TiO2 solution onto substrate
radiation. This characterization provide precise
information about crytallinity phases and
crystallite size of nanostructured TiO2 thin film. Drying

2.4.2. Atomic force microscope (AFM) Annealing

The nanostructured TiO2 thin film was

characterized with atomic force microscope Characterization method:
(AFM XE-100) at room temperature. With non- •Atomic force microscope (AFM)
Figdiffraction
•Xray 1. Experimental
(XRD)chart
contact cantilever and non-contact mode, this
•IV analysis
characterization method promises a non-
destructive testing. Other than that, it also
capable to give the information about grain size Figure 1. Experimental procedure.
and roughness of nanostrutured TiO2 thin film.
We scan the TiO2 thin film of area 500 nm x 3. RESULT AND DISCUSSION
500 nm.
3.1. Effect of annealing process
2.4.3. IV analysis
Figure 2 shows the XRD spectra of TiO2 thin
Current-Voltage (IV) measurement was film before and after the annealing process at
performed to investigate the electrical 500°C for 1 hour. The TiO2 thin film was
properties of nanostructured TiO2 thin film. coated for 5 layers. After annealing process, the
The IV measurement was performed with using XRD peaks was shown at 25.3°, 37.8° and
2-point probe connected to a source meter 48.06° correspond to the anatase peak at (101),
(Keithley 2400). The data of IV characteristic (004) and (200) crystal planes of
was plotted with platinum (Pt) as the metal nanostructured TiO2 thin film, respectively. In a
contact. From the IV curve, the information of previous report, it has been showed that the
resistivity can be obtained from the equation electronic and optical property of anatase phase
below: was making it chosen for DSSCs rather than
rutile and brokite phase [9]. Figure 2 shows that
the TiO2 thin film after the annealing process is

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better than before the annealing process. Table 1 : Resistance and resistivity of TiO2 thin
film before and after annealing process
[101]
Before anneal After anneal
Intensity (a.u)

[211] Resistance
[004] 5.00E+08 8.00E+07
[200] (Ω)
Thickness
After anneal 0.5 0.4
(μm)
Before anneal Resistivity
2.34E+04 3.20E+03
20 25 30 35 40 45 50 (Ω . cm)
2 Degree)
Table 1 shows the resistivity of TiO2 thin
Figure 2. XRD spectra of TiO2 thin film before film before and after the annealing process. It
and after annealing process. was noticed that the resistivity was decreased
after annealing process as compared with as-
prepared before annealing process. This may be
(a) due to the reason where after annealing
process, the good crystallinity and
nanostructure surface area obtained after the
annealing and it promises much surface for
electron passes through from one grain to
another grain within the TiO2 thin film.

3.2. Effect of thickness

(b) The thickness of nanostructured TiO2 thin
film can be control through controlling times
repeating of coating TiO2 solution onto
substrate. The thickness of film were
approximately 0.2 μm, 0.4 μm and 1.0 μm with
1, 5 and 10 layer of TiO2 thin film,
respectively. Under the XRD spectra, with
increasing number of layer, the anatase peak of
TiO2 can be identified clearer. The crystallinity
of TiO2 was identified best at 5 layers and
Figure 3. AFM image of TiO2 thin film (a)
above (figure 4).
before and (b) after annealing process.

Figure 3 shows the surface morphology of

TiO2 thin film before and after the annealing [101]

processes. The roughness of thin film increases

Intensity (a.u)

from 0.341 to 1.690 after the annealing process. [004] [200]

The increase in roughness is due to the existing
of larger grain size of nanostructured of TiO2 10 layer
[211] 5 layer
thin film which can be seen in figure 3 (b).
1 layer

20 25 30 35 40 45 50
2   Degree)

Figure 4. XRD spectra of 1, 5 and 10 layer of

nanostructured TiO2 thin film after annealing
process.

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Table 2 : Resistance, sheet resistance and

(a) resistivity of 1,5 and 10 layer of TiO2 thin film
after annealing process.

1 layer 5 layer 10 layer

Resistance
5.00E+07 8.00E+07 8.00E+08
(Ω)
Thickness
0.2 0.4 1
(μm)
(b) Resistivity
1.00E+03 3.20E+03 8.00E+04
(Ω . cm)

3.3. Effect of amount of solvent

One of the key parameter for TiO2 thin film

as an electrode in DCCS is that it needs to be
(c)
transparent. This can be control by changing
the concentration of sol. We varied the amount
of ethanol solvent between 20% and 70% for
this study. In general, we found that the TiO2
thin film using 20% of ethanol was transparent
compared to 70% of ethanol.

Figure 5. AFM image of (a) 1, (b) 5 and (c) 10

layer of TiO2 thin film. [101]

Figure 5 shows the surface morphology

Intensity (a.u)

of TiO2 thin film for different layers. The [211]

measured roughness was 1.574 nm, 1.690 nm [004] [200]
and 1.794 nm for 1, 5 and 10 layers,
respectively. The roughness of TiO2 thin film
20 %
increased with the thickness of TiO2 thin film.
Table 2 shows the electrical properties
70 %
of TiO2 thin film for 1, 5 and 10 layers. With
the increasing in the number of layer, the 20 25 30 35 40 45 50
resistance and resistivity increased [11]. This is
due to when we increase number of layer, the 2  (Degree)
electron need to passes through the film with
longer time to complete the circuit during the I- Figure 6. XRD spectra of 20% and 70%
V measurement. amount of ethanol.

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Table 3 : Resistance, sheet resistance and

(a) resistivity of 10% and 70% of TiO2 thin film
after annealing process.

20% ethanol 70% ethanol

Resistance
8.00E+07 5.00E+07
(Ω)
Thickness
0.4 0.458
(μm)
(b) Resistivity
3.20E+03 2.29E+03
(Ω . cm)

7. CONCLUSION
We have successfully fabricated the TiO2
thin film at various thickness and amount of
solvent along with annealing process. The
Figure 7. AFM image of (a) 20% and (b) 70% effect of the growth condition to the
amount of ethanol crystallinity, morphology and IV properties has
been studied.
Figure 6 shows the XRD analysis of TiO2 We found that the annealing process and
thin film using 20% and 70% of ethanol the number of layer influence the crytallinity
solvent. The peak of anatase TiO2 is decreased and morphology of TiO2 thin film. The
with the increasing amount of ethanol. The annealing process gives anatase phase of
XRD spectra of nanostructured TiO2 thin film nanostructured TiO2 thin film appears in XRD
with 70% amount of ethanol shows single peak spectra. The anatase peak of nanostructured
of anatase compared to nanostructured TiO2 TiO2 thin film can be identified clearer with
thin film with 20% amount of ethanol. increase number of layer.
Figure 7 shows the AFM images of thin film Roughness of TiO2 thin film is increase
prepared using 20% and 70% amount of with annealing process and number of layer but
ethanol. The roughness was 0.625 at 70% decrease with increasing amount of ethanol.
amount of ethanol. On the other hand, the The resistivity of TiO2 thin film decrease
roughness increased to 1.690 at 20% amount of with annealing process and amount of ethanol
ethanol. but increase with the number of layer deposited
Table 3 shows the electrical properties of on nanostructured TiO2 thin film.
TiO2 thin film with 20% and 70% ethanol. The Finally, we propose that the TiO2 thin film
resistivity slightly increased when the 20% of is good to growth with annealing process, 5
ethanol was used. This is clearly understood layer and 20% amount of ethanol. However,
from figure 6 where one can see a single phase further investigation on the optical properties of
structure of TiO2 thin film. The single phase this TiO2 thin film is needed.
structure enhances the electron mobility thus
improve the conductivity [10]. Therefore, the
resistivity is lower at 70% of amount ethanol. ACKNOWLEDGMENT
The authors would like to thank Universiti Tun
Hussein Onn Malaysia (UTHM) for supporting
this research under the Postgraduate Incentive
Research Grant and Ministry of Higher
Education for Fundamental Research Grant
Scheme, Phase 2/2009. We also thank Mr
Tarmizi and Mr Anuar of Faculty of
Mechanical and Manufacturing Engineering of
UTHM for XRD analysis.

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