CHAPTER 1

INTRODUCTION

1.1

Background of study

Metal oxide nanoparticles are getting more attention by many researchers in recent
years due to their special electronic and chemical properties. Among the metal oxide
semiconductors, TiO2 and ZnO have been studied extensively due to their chemical
stability and efficient photocatalytic properties (Stoyanova et al. 2013). Both of these
metal oxides are photoactive, photocatalytically active, and antibacterial. Hence they
are typically used in self-cleaning surfaces, water and air purification, and
bactericidal coatings against microbes.

Titanium dioxide (TiO2) is an oxide of titanium that occur naturally

(Karunaratne 2010). TiO2 is a cheap, harmless, white and non-biodegradable material
(substance that unable to breakdown naturally by the environment or need a long
period of time to breakdown). It is also has a high refractive index, high dielectric
constant, semiconductor properties and chemical stability (El-Nahass et al. 2012).
TiO2 is widely produced as a thin film in the form of nanoparticles to the substrate.
The TiO2 thin film has been studied many years due to their suitability in many
applications.

It is used in photocatalytic activity, photovoltaic cell, and electrochromic

devices. This is due to their biocompatibility, thermal stability, strong oxidized
stability, non-toxicity and long term photostability (Senthil et al. 2010). It is also
used in non electronic devices such as optical brightener in paint, self-cleaning,
ingredient in sun cream, and bone implant. There are three natural phases of TiO2,
which are anatase, rutile, and brookite. The anatase of TiO2 often shows better
photocatalytic activity than rutile form. This has been agreed to the slightly higher
Fermi level of anatase. It has a lower capacity to absorb oxygen and a higher degree
of surface hydroxylation. In the photo-degradation process hydroxyl group on the
surface is very important. This is because in order to produce the very reactive OH
radicals, they directly trap photo-generated holes. Hence oxidize the organic
pollutant. The other indirect role of hydroxyl radical is in producing oxygen radicals
and hindering the electronhole recombination. This hydroxyl radical has a high
oxidization power that is well enough to oxidize and decompose viruses, organic
materials, odour and bacteria.

For most of the photocatalytic decomposition processes in TiO2, photonic

efficiency is relatively low. Furthermore, photocatalytic reactions on TiO2
nanoparticles can usually be induced only by ultraviolet light, which limits the
application of TiO2 as a photocatalyst with visible light It is expected that the
composites of ZnO and TiO2 would exhibit useful applications in photocatalysis. As
to this, recently, several papers that concerned in improving TiO2 photocatalytic
activity have been reported. The nanoparticles of ZnO/TiO2 film would show higher
photocatalytic efficiency than the efficiency of pure nano- ZnO film and nano- TiO2
film.(Benkara et al. 2010)
2

Various technique are used to synthesis thin film of TiO2 and ZnO, including
vacuum evaporation, sputtering, molecular-beam epitaxy, laser-assisted vacuum
evaporation, chemical-bath deposition, electrodeposition, liquid phase deposition, dip
coating and sol gel process (Wang et al. 2013). However, out of these techniques, the
sol gel is considered as the best. This is because, the sol gel process is a liquid
deposit process using soft chemistry that giving homogenous deposit. This process
provides better prospect to deposit film with large surface area (El-Nahass et al.
2012). Beside that, this method is one of the simplest and economical in term of
equipment.

The sol gel process involves spin coating or dip coating of the oxide sol on
substrate. But in this study, we were focuses more on spin coating. Spin coating is
commonly used in the synthesis of TiO2 thin film due to rapid growth rates, capacity
of handling large sample sizes, mass production capability, and high yield rates.

1.2

Problem Statement

In this modern day, there is a problem related to air contamination in our house,
workplace and building. This means, there is pollutant inside the building due to
present of viruses, organic materials, odour and bacteria. Furthermore, the
organisation that uses a lot of space for their building such as university, school,
hospital, and large company must used a lot of expenses for their cleaning equipment
and material.

Therefore, from the previous study TiO2 and ZnO have a lot application such
as photocatalytic activity and self cleaning that is useful to overcome those problems.
3

In addition, TiO2 is a cheap, harmless, white and non-biodegradable material.

Moreover, in this study, we were synthesis the thin film of TiO2 and ZnO
nanoparticles by sol gel spin coating. Where are more economical and lead to
improved performance of the films.

1.3

Significance of Study

The findings obtained at end of this study are significant to other researchers and
industrial practitioners. This is because we use cheaper substance such as TiO2 and
ZnO. Furthermore, we also used sol gel process to synthesis TiO2 and ZnO that is
simple and economical. Hence, would give the chance to produce large surface area
of the coating. Also provide great application in destruction and elimination of
pollutant in air.

1.4

Objectives of the Study

a) To prepare TiO2 particles in solution from hydrolysis Titanium (IV)
Butoxide and prepare ZnO particles in solution from Zinc Nitrate
Hexahydrate by sol gel method.
b) To synthesize thin film of TiO2 sol gel spin coating technique and ZnO
particles by solution-immersion technique.
c) To annealed thin film of TiO2 at temperature 350C, 400C, 450C, 500C
and 550C.
d) Characterization of TiO2/ZnO particles by using UV-Vis (Ultravioletvisible Spectroscopy) and Photoluminescence Spectroscopy ( PL) and
Field Fourier Transform Infrared Spectroscopy ( FT-IR)

CHAPTER 2

LITERATURE REVIEW

2.1

Overview

2.1.1

TiO2

Titanium dioxide (TiO2) have been attracted many researchers due to its suitability in
many application. Such as, semiconductors, separation, catalysis and chemical
protection (Wang et al. 2013). Titanium dioxide has a wide band gap semiconductor
that exhibits high transparency to visible and near infra red (NIR) light (Hinczewski
et al. 2005). It has three crystalline phases: anatase (tetragonal), rutile (tetragonal),
and brookite. Brookite is a naturally occurring phase, and is extremely difficult to
synthesize. Anatase and rutile also occur naturally, but can be synthesized in the
laboratory easily.

TiO2 has a wide band semiconductor. The band gaps of TiO2 are 3.2 eV for
the anatase, , 3.02 eV for rutile and 2.96 eV for brookite phases. (Wunderlich W. et
al.2004). The valence band of TiO2 consists of the 2p orbitals for oxygen hybridized
with the titanium 3d orbitals, while the conduction band is only the 3d orbitals of
titanium. When TiO2 exposed to near-UV light, there is excitation of electrons in the
valence band to the conduction band. Hence, leaves the holes (h+), as shown in

Figure 2.1. Then excited electrons (e) in the conduction band will have purely 3d
state. The transition probability of e to the valence band decreases due to dissimilar
party. This leads to a reduction in the probability of e/h+ recombination.

Anatase TiO2 is considered to be the active photocatalytic component based

on chemical properties, charge carrier dynamics, and the activity of photocatalytic
degradation of organic compounds. Figure 2.2 shows anatase TiO2 has inherent
surface band bending that forms spontaneously in a deeper region with a steeper
potential compared with the rutile phase. Thus, surface holes trapping dominates
because spatial charge separation is achieved by the transfer of photogenerated holes
towards the surface of the particle via the strong upward band bending. However, in
the rutile phase, only holes that very close to the surface are trapped and transferred
to the surface when the bulk recombination of electrons and holes occurs.

Figure 2.1 Mechanism of light absorption by TiO2 (Szaciowski K. et al. 2005)

Figure 2.2 Surface band bending of the (a) anatase and (b) rutile phases of TiO2
(Li G. et al. 2007)

2.1.2. ZnO
Zinc oxide (ZnO) is a chemical compound found naturally in the mineral called
zincite. It has concerning by many researchers recently due to its low cost and able to
obtained by simple techniques (Savi et al. 2012). The techniques is solgel synthesis,
hydrothermal/solvothermal methods, microemulsion method, precipitation,and
physical vapor deposition. In the current study, ZnO nanoparticles was prepared by a
simple and cost effective solgel method (Streams 2011). Sol-gel method gives highpurity, homogenous, and high-quality nanopowders. The changes of solvent will
cause the morphology of the nanoparticles changing.

ZnO is a wide band gap semiconductor, where at room temperature it has an

energy gap of 3.37 eV. It has been used significantly for its catalytic, electrical,
optoelectronic, and photochemical properties. Based on large surface area and high
catalytic activity ZnO nanostructures, it will be beneficial to be apply to a catalytic
reaction process.(Kumar et al. 2013)

2.2

Chemical structure

2.2.1

TiO2

TiO2 is from the family of transition metal oxides. There are three generally known
polymorphs of TiO2 found in nature: anatase (tetragonal), brookite (orthorhombic),
and rutile (tetragonal). Other than these polymorphs, there are two additional highpressure forms have been synthesized from the rutile phase. These are TiO2 (II) with
a PbO2 structure and TiO2 with a hollandite structure.

Rutile TiO2 has a tetragonal structure and contains 6 atoms per unit cell
(Figure 2.3). The TiO6 octahedron is slightly distorted. The rutile phase is stable at
most temperatures and pressures up to 60 kbar, where TiO2 (II) becomes the
thermodynamically favorable phase. It is found that anatase and brookite structures
transformed to the rutile phase after reaching a certain particle size. Where the rutile
phase becoming more stable than anatase when particle sizes greater than 14 nm
(Zhang et al.2000). Once the rutile phase formed, it grew more rapidly than the
anatase. The photocatalytic activity of the rutile phase is usually very poor. However,
it can be concluded that the rutile phase can be active or inactive, which depend on
its preparation conditions.

Anatase TiO2 also has a tetragonal structure but the distortion of the TiO6
octahedron is slightly larger for the anatase phase, as depicted in Figure 2.4. The
anatase phase has been reported to develop at temperature below 800 oC which at
higher temperatures transform to the more stable rutile phase (Mechiakh et al. 2011).
The anatase structure is favourable than the other polymorphs for solar cell
applications. This is because of its low dielectric constant, high electron mobility,
8

and lower density. The slightly higher Fermi level that has low capacity to adsorb
oxygen and higher degree of hydroxylation in the anatase phase causes an increased
in photoreactivity. Brookite of TiO2 belongs to the orthorhombic crystal system. The
unit cell TiO2 has 8 formula units and is formed by edge-sharing TiO6 octahedra
(Figure 2.5). It is more complicated, has a larger cell volume and is also the least
dense of the 3 forms and is not often used for experimental investigations (Thompson
et al, 2006).

Table 2.1 Crystal structure data for TiO2 (Gupta and Tripathi 2011)
Properties

Anatase

Rutile

Brookite

Crystal structure

Tetragonal

Tetragonal

Orthorhombic

Lattice constant ()

a = 4.5936

a = 3.784

a = 9.184

c =2.9587

c = 9.515

b = 5.447
c = 5.154

Molecule

Density (g cm-3)

4.13

3.79

3.99

TiO bond length

1.949

1.937

1.872.04

()

1.980

1.965

OTiO bond angle

81.2

77.7

90.0

92.6

Figure 2.3 Crystal structure of rutile

77.0105

Figure 2.4 Crystal structure of anatase

Figure 2.5 Crystal structure of brookite

2.2.2

ZnO

ZnO crystallizes in the structure of wurtzite. Where each anion is bounded by four
cations at the corners of a tetrahedron, and vice versa ZnO is available as large bulk
single crystals. This tetrahedral coordination is usual of sp3 covalent bonding nature.
The present of substantial ionic character in the material tends to increase the band
gap further than expected from the covalent bonding. ZnO is a IIVI compound
semiconductor whose ionicity resides at the borderline between the covalent and
ionic semiconductors. The crystal structures of ZnO are wurtzite (B4), zinc blende
10

(B3), and rocksalt (or Rochelle salt) (B1) as schematically shown in Figure
2.6.(Properties 2009)

Figure 2.6 Crystal structures of ZnO

2.3

Properties of TiO2 & ZnO

2.3.1

Physical properties

Solutes will affect the solubility of titanium dioxide. It is soluble in hot concentrated
sulphuric acid, hydrochloric acid, nitric acid, but insoluble in dilute alkali and dilute
acid. Titanium dioxide has the performance of the semiconductor. Increasing
temperature will increase the conductivity rapidly. It is also very sensitive to
hypoxia. The melting and boiling points of the board of rutile and anatase titanium
dioxide in fact does not exist. This is because, when anatase and plate titanium
dioxide are at high temperatures, it can be transformed into rutile. Titanium dioxide
has a good thermal stability, the general amount of 0.01% to 0.12%. Furthermore,
titanium dioxide has not too strong hydroscopicity. Where, the hydrophilic is
connected to surface area. The large the surface area, provide greater moisture
11

absorption. The moisture absorption of titanium dioxide is related to the surface

treatment and the nature too.

Zinc oxide crystallizes in two major forms, hexagonal wurtzite and cubic
zincblende. The wurtzite structure is most stable at ambient conditions and thus most
common. The growing of ZnO on substrates with cubic lattice structure able to
stabilized zincblende form. The zinc and oxide centers are tetrahedral in both cases,
the general characteristic geometry for Zn(II). At relatively high pressures about 10
GPa, ZnO converts to the rocksalt motif. Polymorphs of hexagonal and zincblende
do not have inversion symmetry (reflection of a crystal relative to any given point
does not transform it into itself). This and other lattice symmetry properties result in
piezoelectricity of the hexagonal and zincblende ZnO, and pyroelectricity of
hexagonal ZnO.

2.3.2

Chemical properties

Titanium dioxide is non-toxic and has stable chemical properties. Under normal
temperature, it almost has no reaction with other material. There is no reaction with
oxygen, hydrogen sulphide, sulphur dioxide, carbon dioxide and ammonia. It is also
insoluble in water, fatty acids, other organic acid and weak inorganic acid except for
alkali and hot nitric acid. But, in several specific conditions, titanium dioxide is able
to react with some substance.

For example, these reactions as follows:

1) TiO2 can only totally soluble in the condition of long time boiling in strong
sulphuric acid and hydrofluoric acid. The reaction equation is as follows:
12

TiO2+ 2H2SO4 = Ti (SO4)2 + 2H2O

TiO2+ H2SO4 = TiOSO4 + H2O
TiO2 + 6HF = H2TiF6 + 2H2O
2) Titanium dioxide can melt in the alkali (sodium hydroxide, potassium
hydroxide) or alkali metal carbonate (sodium carbonate, potassium carbonate).
Any one of which is have stated with titanium dioxide can be transformed into
soluble acid titanate.
For example, Titanium dioxide and sodium hydroxide's reaction equation:
TiO2 + 4NaOH = Na4TiO4 + 2H2O
3) At high temperature, the present of reductant (carbon, starch, petroleum
coke), results in chlorinationof titanium dioxide into titanium tetrachloride by
chlorine. The response equation is as follows:
TiO2 +2C +2Cl2 = TiCl4 + 2CO
4) Titanium dioxide under high temperature can be restored into Low-valent
titanium compounds by hydrogen, sodium, magnesium, aluminum, zinc,
calcium, and some elements of the constant. Ti2O3 will be obtained if the dry
hydrogen is put into red titanium dioxide. In 2000 and 15.2 MPa of hydrogen,
it also can get TiO. The injection of rutile titanium dioxide into the plasma
chamber, will be reduced it into titanium metal through hydrogen. Three reaction
equations are as follows:
2TiO2 + H2 = Ti2O3 + H2O
TiO2 + H2 = TiO + H2O
TiO2 + 2H2 = Ti + 2H2O
Crystalline zinc oxide is thermochromic, changing from white to yellow when
heated and in air reverting to white on cooling.
13

Zinc oxide is an amphoteric oxide. It is almost insoluble in water, but it is

soluble in (degraded by) most acids, such as hydrochloric acid:
ZnO + 2 HCl ZnCl2 + H2O
ZnO is a considerably stable compound. It has a melting point around 1975
degree celcius in which it decomposes into Zinc Vapor and Oxygen.

2.4

Nanoparticles of titanium dioxide and zinc oxide

Various investigations have recognized that TiO2 is much more effective as a

photocatalyst in the form of nanoparticles than in bulk powder (Han H, Ba R. 2009).
When the diameter of the crystallites of a semiconductor particle falls below a
critical radius of about 10 nm, each charge carrier appears to behave quantum
mechanically as a simple particle in a box. As a result of this confinement, the band
gap increases and the band edges shift to yield larger redox potentials. However, the
solvent reorganization free energy for charge transfer to a substrate remains
unchanged.

Mill and Le Hunter (1997) reported that decreasing particle size resulted in
absorption edge blue shifts, the redox potentials of the photogenerated electrons and
holes in quantized semiconductor particles increased. Means, quantized particles
show

higher

photoactivity

than

macrocrystalline

semiconductor

particles.

Futhermore, TiO2 has been prepared in the form of powders, crystals, thin films,
nanotubes and nanorods. Liquid phase processing is one of the most suitable and
frequently used methods in chemical synthesis. This method has the advantages of
controlling the stoichiometry, homogeneous products and allowing the formation of
complex shapes and preparation of composite materials.
14

2.5

Study of TiO2 and ZnO thin films with the same parameters.

2.5.1

Surface Morphologies and photocatalytic activity of TiO2 thin film

annealed at different temperature by AFM

TiO2 thin film was synthesis using spin coating technique at different annealing
temperature. The study is to determine the optimal annealing temperature, that able
to produce the most excellent photocatalytic performance. Atomic force microscopy
(AFM) was used to determine the surface roughness. While the thin film optical
properties of were determine by UV-VIS spectroscopy (PerkinElmer). The starting
material in this study is titanium isopropoxide (TIP).

From the AFM images and data, as shown in Table 2.2, it show that for the
crystalline films, increasing annealing temperature causes slightly increased of the
grain size and significantly increased the surface roughness. But the thickness of the
film remained at ~255 nm, regardless of the annealing temperature. All of the films
were highly transparent in the visible region (~80%), the optical indirect band gap
decreased slightly with increasing annealing temperature. For the total range films,
the increased annealing temperature to 400 C show the increased of photocatalytic
performance. But, after increase to higher temperature the performance was observed
to decrease. Thus, it concluded that for an annealing time of 2 hour, 400C is the
optimal temperature for annealing TiO2 thin film. (Lin et al. 2013)

15

Table 2.2 Analytical data

Parameter

Annealing temperature (oC)

Units

300

400

500

Mineralogy

Amorphous

Anatase

Anatase

Average grain size

Nm

~10

~23

~29

Arithmetic surface roughness

Nm

0.32

0.59

0.96

Film thickness

Nm

~260

~250

~246

Transmission in visible range

~80

~80

~80

Optical indirect band gap

eV

3.49

3.49

3.43

Figure 2.7 Images of AFM with different annealing temperature

16

2.5.2

Influence of Annealing Temperature on the Photoluminescence Property

of ZnO thin film covered by TiO2 nanoparticles

Fig. 2.8 shows the photoluminescence spectra of TiO2ZnO thin films and the bare
ZnO thin film.For the bare ZnO thin film, it has an ultraviolet emission peak centered
at 384 nm. This originates from the recombination of free exciton. There is also
present of wide and weak green emission band. The emission mechanism of green
emission behaviour of ZnO material is unclear yet although it has been widely
studied. There are suggestions from several researchers where the green emission is
probably related with oxygen vacancy defect in ZnO materials.

The results show the ultraviolet emission of ZnO thin films is greatly
improved after they are covered by TiO2 nanoparticles, while the green emission is
hidden. At pretty high annealing temperature (more than 500 C), the intensity of
ultraviolet emission will decrease and a violet emission peak along with a blue
emission peak appears. This is probably related with the atomic interdiffusion
between TiO2 nanoparticles and ZnO thin

film. Hence, choosing a suitable

annealing temperature is a main factor to obtain the most efficient ultraviolet

emission from TiO2ZnO thin film. (Xu et al. 2010)

17

Figure 2.8 Photoluminescence spectra of the bare ZnO thin film and TiO2ZnO thin
films.

2.6

Photocatalytic activity

In chemistry, the presence of a catalyst will accelerated the photoreaction of

photocatalysis. The light is absorbed by an adsorbed substrate in catalysed
photolysis. In photogenerated catalysis, the photocatalytic activity (PCA) depends on
the ability of the catalyst to create electronhole pairs, which generate free radicals
(e.g. hydroxyl radicals: OH) that able to undergo secondary reactions.

For photocatalytic oxidation (PCO), it is occurs when UV light rays is join

with a TiO2 coated filter. Where creating hydroxyl radicals and super-oxide ions, that
are extremely reactive electrons. These extreme reactive electrons will violently
combine with other elements in the air, such as bacteria and volatile organic
compounds (VOCs). Where include unsafe pollutants such as ammonia,
formaldehyde and many other regular contaminates that released by building
materials and household cleaners generally found in the home.

18

The chemical reaction is occurred between the super-charged ion and the
pollutant after bound together and efficiently "oxidizing" (or burning) the pollutant.
The pollutant will breaks down into non dangerous carbon dioxide and water
molecules. Hence, makes the air more purified.

Figure 2.9 Principle of Photo-catalytic Oxidation

ZnO are most extensively used semiconductor photocatalysts due to their

high photosensitivity, photochemical stability, large band gap, strong oxidizing
power and non-toxic nature.

19

CHAPTER 3

METHODOLOGY

3.1

Chemical:

TiO2 solution
1.

Titanium (IV) Butoxide, reagent grade, 97% AIDRiCH.

2.

Glacial Acetic Acid (GAA), Glacial (CH3COOH), (J.T. BAKER)

3.

Triton-X. (J.T. BAKER)

4.

Ethyl alcohol.

ZnO solution
1.

Zinc Nitrate Hexahydrate

2.

Hexamethylenetetramine (HMTA)

3.2

Apparatus:

1.

Glass substrate

2.

Measuring cylinder (100 mL)

3.

Beaker (250 mL & 50 mL)

4.

Schott bottle (100 mL)

5.

Magnetic stirrer

6.

Sample container

7.

Sample box

8.

Tweezer

9.

Reaction bottle
20

3.3

Preparation of Glass Substrate:

The glass substrate of microscope is cut into 3 pieces using the diamond cutter, with
the size of approximately 2.0 cm 2.0 cm for each piece. Methanol, acetone and DI
water is used to clean the glass substrates (so that no extraneous particles on their
surfaces) by using Ultrasonic bath for 5 minutes at 40 C.
i. Methanol : 2 times
ii. Acetone: 2 times
iii. DI water: 2 times
The wet glass substrates is then dried out using hair dryer and put into a sample
container.

3.4

Preparation of TiO2 Structures:

22.203 mL Ethanol + 4.254 mL TTiB + 1.250 mL GAA + 1 drop Triton X-100 +

0.090 mL DI water and lastly 22.03 mL ethanol was added again into a 100mL
schott bottle at 60C with continuous stirring to prepare 0.25 M of TiO2 solution.
After 2 hours, the heat was turned off and stirring is continued for 22 hours.

3.5

Deposition of TiO2 Structures:

TiO2 thin films were deposited using sol-gel spin coating method. The deposition of
TiO2 on the glass substrate required 15 drops of TiO2 sol gel for each layer. Where in
this study each samples prepared is coated with 7 layer of TiO2 sol gel. This method
involves three steps, which are:
a.

Step 1: time= 10 s, speed= 3000 rpm

b.

Step 2: time= 30 s, speed= 6000 rpm

c.

Step 3: time= 10 s, speed= 2000 rpm

21

For each layer of TiO2, the film was heated in an oven at 150 C for 10 minutes. The
sample was annealed in annealing chamber at 350 C, 400 C, 450 C, 500 C and
550 C for 2 hours.

3.6

Preparation of ZnO Structures:

1.4875 g of Zinc Nitrate Hexahydrate was dissolved in 100 mL of DI water. 0.7012 g

of Hexamethylenetetramine (HMTA) was dissolved in 100 mL of DI water. Then,
the HMTA solution was added into Zinc Nitrate Hexahydrate solution and was
mixed well. The zinc solution is then transferred into a schott bottle and the beaker
containing solution must carefully rinsed with another 50 mL of DI water to make
sure no solution is left. The ZnO solution was heated at 60 C with continuous stirrer.
After 2 hours, the heat was turned off and stirring is continued for 22 hours.

3.7

Deposition of ZnO Structures:

The glass substrate that has been coated with TiO2 was placed in the reaction bottle.
Then the glass substrate was immersed in ZnO solution and the reaction bottle is
capped. The reaction bottle is placed in water bath at 90 C for 4 hours. After 4
hours, the ZnO solution is removed and the glass substrate was rinsed with DI water
before heated in the oven at 150 C for 20 minutes. The sample was annealed in the
annealing chamber at 500 C for 1 hour.

3.8

Characterization of TiO2 Structures:

3.8.1

UV-Vis

Ultraviolet (UV) and visible radiation consist of only a small part of the
electromagnetic spectrum.

Electromagnetic
22

radiation

can

be

considered

combination of alternating electric and magnetic fields that travel through space with
a wave motion. Because radiation acts as a wave, it can be classified in terms of
either wavelength or frequency. When light passes through or is reflected from a
sample, the amount of light absorbed is the difference between the incident radiation
and the transmitted radiation. The amount of light absorbed is expressed as either
transmittance or absorbance. Ultraviolet-visible spectroscopy is used to determine
the optical properties of the thin film TiO2/ZnO structures.(Upstone 2000)

3.8.2

Photoluminescence Spectrosccopy (PL)

Photoluminescence spectroscopy is a contactless, non-destructive method of probing

the electronic structure of materials. The absorption of light causes the photoexcitation process occurs when the light is directed to the sample. In this process, the
material jumps to a higher electronic state and when in relaxes it will release the
energy as photon and then return back to a lower energy level. This emission of light
is called photoluminescence (PL). PL is used to investigate the impurity level and
defects, recombination mechanism and quality of material.(C.Li 2006)

3.8.3

Fourier Transform Infrared (FT-IR)

Infrared spectroscopy is to study the interactions between matter and electromagnetic

fields in the infrared region. In this spectral region, the electromagnetic waves
mainly couple with the molecular vibrations. Which is by absorbing IR radiation, a
molecule are able to excite to higher vibrational state. The probability of a particular
IR frequency being absorbed depends on the actual interaction between this
frequency and the molecule. Generally, a frequency will be strongly absorbed if its
photon energy coincides with the vibrational energy levels of the molecule .The
23

resulting spectrum shows the absorption and transmission of molecular. Hence,

creates a molecular fingerprint of the sample. Like a fingerprint no two unique
molecular structures produce the same infrared spectrum. (Nicolet et al. 2001).

24

CHAPTER 4

RESULT AND DISCUSSION

4.1

Characterization of TiO2/ZnO Structures

4.1.1

UV-Vis Results of TiO2/ZnO Structures

Figure 4.1 shows the optical transmittance for different annealing temperature of
TiO2/ZnO thin film which is measured in the range of wavelength 200-850 nm. The
transmittance spectra show that all film had average transmittance between 1% to
80% within the visible region (400-850 nm). The transmission decreases sharply near
the ultraviolet region about 380 nm due to the band gap absorption.

It is also found that the as-grown of TiO2/ZnO thin film has the highest
transmittance compare to the others. As-grown is the thin film that has the layer
coated with TiO2 which did not undergo any annealing process before being coated
with ZnO. The transmittance for the as-grown is about 80%. While, for all of the film
analyzed it is observed that the increase of annealing temperature would decrease the
optical transmission. To be specific, the thin film that was annealed at 350C, 400C
and 450C has similar pattern of transmittance. All of these films start to transmit at
the wavelength 300 nm.

While, the films annealed at temperature 500C to 550C behave differently.

It starts to transmit at the wavelength of 500 nm. Based on this observation, it can be
assume that there are changes in the structure of the thin films when annealed at

25

different temperature. As it is obviously seen the thin films annealed at temperature

500C and above have the transmission differ from the other.

However, overall the increased of annealing temperature has the effect of

lowering the transmittance. It is might be due to the increased of the film surface
roughness and increase light scattering on the surface when annealed at certain
temperature. The increase in surface roughness also means that there is decrease in
the films transparency (Firdaus et al. 2012). The low transmittance in visible range
causes light scattering on rough surface of thin film as the particle is less uniformly
dispersed on the glass substrate due to formation of large agglomerated particle. As
obtained in the result, starting at annealing temperature of 500C and above the
transmittance of the thin film is very low. Means starting temperature of 500C the
structures of the compound begin to change and became rough which causing the
light to scattered. Hence, decrease the film transparency.
as-grown
350
400
450
500
550

80

as grown

% Transmittance

60

350 C
o

550 C
o
450 C
o
500 C

40

400 C
20

200

300

400

500

600

700

800

Wavelength / nm

Figure 4.1: Ultraviolet- visible transmittance spectra of TiO2/ZnO with

different annealing temperature
26

Figure 4.2 shows that the absorption of TiO2/ZnO thin film increase with
increase of annealing temperature from 350C to 550C. All the thin film annealed
starts to absorb light at the wavelength of 300 nm. The absorption for all thin film in
the ultraviolet range is relatively high which is at the intensity of 6 arbitrary unit, but
then decrease gradually in the visible region. Where, the absorption is actually
inversely proportional to the transmittance. This might be related to the increase in
grain size which contributes to the light scattering effect due to the high surface
roughness.

as-grown
350
400
450
500
550

6
o

500 C
o

Absorbance (a.u.)

550 C
4

400 C
o

450 C
o

350 C
as-grown

400

600

800

Wavelength / nm

Figure 4.2: Ultraviolet- visible absorbance spectra of TiO2/ZnO with

different annealing temperature

4.1.2

Photoluminescence Spectroscopy (PL)

Figure 4.3 shows there are two types of peak emission, which are ultraviolet peak
emission and visible peak emission. The peak of ultraviolet can be seen near the
ultraviolet region about 380 nm.

Figure 4.3 also shows that the increase of

27

annealing temperature will increase the ultraviolet emission until it reaches 450C.
However, the ultraviolet emission is reduced when the annealing temperature
increase from 5000C to 5500C (Xu et al. 2010).

Figure 4.4 shows the enlargement of Figure 4.3 which focuses on the peak at
the UV region within the wavelength of 350 nm 450 nm. It is observed there is a
red-shift occurred as the temperature increased from 350C to 450C. The increase of
annealing temperature from 350C, 400C and 450C shows the peak emission will
shifted at 382 nm, 387 nm and 392 nm respectively. However, at the annealing
temperature 500C and 550C there is no shifted occur as it has peak relatively
similar as 350C. This means the increased of annealing temperature might cause
red-shift. Red-shift is occurs usually due to decrease of the band gap cause by the
increase in particle size. (Epitaxy 2001).

Figure 4.5 and 4.6 is plotted based on information obtained from Figure 4.3
by using temperature versus intensity. It differentiates between the peak emission of
UV region and the peak emission of visible region. From both of this figures, it
shows that the increase of annealing temperature on thin film from 350C to 450C
will increase the PL peak for both of UV and visible region. However, further
increase of annealing temperature from 500C to 550C will decrease the PL peak for
both of the region.

From the observation obtained, it obviously shows that the increase of

annealing temperature on thin film of TiO2/ZnO structures will increase the peak
emission until certain temperature. Here, in this study, PL peak emissions increase as
28

the temperature increases until 450C. The increase in PL peak emission is deduced
due to quality improvement of crystal after being annealed (Du n.d.).While further
increase of annealing temperature up to 500C and above shows the decreases of PL
peak emission. The crystalline quality of TiO2/ZnO decrease when the annealing
temperature increased up to 500C and above (Xu et al. 2010) Based on this
observation, the optimum annealing temperature for the synthesis of TiO 2/ZnO thin
film nanostructures is 450C.
as-grown
350
400
450
500
550

350
300
o

450 C

Intensity (a.u.)

250
200
150

400 C

100

350 C
o

500 C

50

550 C
as-grown

0
300

400

500

600

700

800

900

wavelength / nm

Figure 4.3 PL result of TiO2/ZnO with different annealing temperature.

as-grown
350
400
450
500
550

50
45
o

450 C

40

Intensity (a.u.)

35

as-grown

30
o

25

400 C
o
550 C
o
500 C

20
15

350 C

10
5
0
350

360

370

380

390

400

410

420

430

440

450

wavelength / nm

Figure 4.4 PL result of TiO2/ZnO with different annealing temperature on

UV region
29

50
45
40

Intensity (a.u.)

35
30
25
20
15
10
5
0

50

100

150

200

250

300

350

400

450

500

550

Annealing Temperature ( C)

Figure 4.5 PL emission of TiO2/ZnO thin film in UV region at various

annealing temperatures (wavelength 380 nm 400 nm)

350
300

Intensity (a.u.)

250
200
150
100
50
0
0

100

200

300

400

500

600

Annealing Temperature ( C)

Figure 4.6 PL emission of TiO2/ZnO thin film in visible region at various

annealing temperatures (wavelength 450 nm 800 nm)

30

4.1.3

Fourier Transform Infrared (FT-IR)

Figure 4.7 shows the FT-IR result of TiO2/ZnO thin film annealed with different
temperatures. All the films are analyzed in the wavenumber range of 400-4000 cm-1.
It is observed there is no absorption band from 1200 cm-1 to 4000 cm-1. Then, the
observation is conducted again by using the wavenumber range at 400 cm -1 to 1050
cm-1 as shown in Figure 4.8. The reduce of the wavenumber range is to analyzed the
absorption band more clearer, as there is no absorption band observed at the range
higher than 1200 cm-1.Figure 4.8 shows the present of strong absorption band for all
thin film of TiO2/ZnO at 540 cm-1 which assigned for Ti-O-Ti bond.(Sonone 2014)
There is also absorption band observed at 460 cm-1 that assigned as zinc oxide bond.

Based on this observation, it is assumed all the thin film of TiO2/ZnO that
coated with annealing temperature from 350C to 550C does not contain any
organic bonding such as aliphatic, C-C bond, alkyl, C-H bond and hydroxyl bond, COH. The thin films of TiO2/ZnO will also not have the hydroxyl bond because all of
the film has undergo annealing process.(Merouani 2008). This means during
annealing process the moisture has been lost. However, it is deduce that there is no
interaction between the chemical structures of TiO2 and ZnO. This might be due to
different layer of coating. As TiO2 layers is coated first then followed by ZnO layer.
Table 4.1 contain the chemical bond and their wavenumber that related to the
nanocrystalline of TiO2/ZnO.

31

as-grown
350
400
450
500
550

110

105

as-grown
o

550 C
o
500 C

100

Intensity (au)

350 C
o

450 C

95

90

400 C

85

80
400

800

1200

1600

2000

2400

2800

3200

3600

4000

-1

Wavenumber (cm )

Figure 4.7: FT-IR result of TiO2/ZnO with different annealing temperature

(Wavenumber 350 cm-1-4000 cm-1)

as-grown
350
400
450
500
550

150
o

550 C

140

400 C

130

Intensity (a.u.)

500 C
120

450 C

110

350 C
as-grown

100
90
80
70
400

500

600

700

800

900

1000

-1

Wavenumber (cm )

Figure 4.8: FT-IR result of TiO2/ZnO with different annealing temperature

(Wavenumber 350 cm-1-1050 cm-1)

32

Table 4.1 Chemical bond and their wavenumbers in FTIR spectra.

Chemical Bond

Wavenumber (cm-1)

N-H stretch

3443

C-H stretch

2969

C-H stretch

2925

C=O stretch

1685

ZnO stretch

460-470

TiO2 stretch

510-540

33

CHAPTER 5

CONCLUSION AND RECOMMENDATION

3.8

Conclusion

The structured of TiO2/ZnO thin film are prepared by sol-gel spin coating technique
on the glass substrate. Firstly,the glass substrate is coated by TiO2 film and annealed
with different temperature. Only then, ZnO film is coated on the TiO2 film and
forming TiO2/ZnO thin film. Here the effect of annealing temperature on optical
properties is studied by using UV-Vis, photoluminescence (PL) and FT-IR
measurement. The variation of annealing temperature contributes a great effect on
the optical properties of TiO2/ZnO structures.

From the UV-Vis result, it reveals that the increased of annealing temperature
on the thin film of TiO2/ZnO structures will causes a decrease in the transmittance at
the ultraviolet region and conversely cause an increase in thin film absorbance.

Based on PL result, the increased of annealing temperature will increased the

photoluminescence peak with temperature from 3000C to 4500C. As the temperature
increase further the photoluminescence peak will decrease. So, we can conclude that
450C is the optimum annealing temperature to synthesize thin film of TiO2/ZnO.

While at the ultraviolet region there is shifted of PL peak from 385 nm to 395
nm at annealing temperature 350C to 450C. This indicates the present of red shift.
34

Hence, the decrease of the optical band gap maybe due to the increase of crystalline
structure.

In the FT-IR measurement, all of the thin film shows a strong adsorption band
near 540 cm-1. This reveals the vibration properties of TiO2. There is also presence of
absorption band at 460 cm-1 which indicates the vibration properties of ZnO. There is
no absorption band found at the range of 2000 cm-1 to 4500 cm-1. This means there is
no organic compound present in the thin film. The hydroxyl bond also not present,
the moisture has been removed during the annealing process.

3.9

Recommendation

This present work is only focused on the optical properties of TiO2/ZnO

nanostructures. The better result and understanding might be obtained if focused on
the other properties such as electrical properties, structural properties and surface
morphology. The optimum annealing temperature obtained by this study for
synthesis

TiO2/ZnO

nanostructures

can

35

also

be

used

in

the

future

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38

APPENDICES

1.

Figures of ultraviolet-visible transmittance spectra of TiO2/ZnO with

different annealing temperatures.

as-grown
350
400
450
500
550

80

as grown

% Transmittance

60

350 C
o

550 C
o
450 C
o
500 C

40

400 C
20

200

300

400

500

600

700

800

Wavelength / nm

Figures of ultraviolet-visible absorbance spectra of TiO2/ZnO with different

annealing temperatures

as-grown
350
400
450
500
550

6
o

500 C
o

550 C

Absorbance (a.u.)

2.

400 C
o

450 C
o

350 C
as-grown

400

600

Wavelength / nm

39

800

3.

PL

result

of

TiO2/ZnO

with

different

annealing

temperature

as-grown
350
400
450
500
550

350
300
o

450 C

Intensity (a.u.)

250
200
150

400 C

100

350 C
o

500 C 550oC

50

as-grown
0
300

400

500

600

700

800

900

wavelength / nm

4.

FT-IR results of TiO2/ZnO with different annealing temperature.

as-grown
350
400
450
500
550

110

105

as-grown
o

550 C
o
500 C

Intensity (au)

100

350 C
o

450 C

95

90

400 C

85

80
400

800

1200

1600

2000

2400

2800
-1

Wavenumber (cm )

40

3200

3600

4000

CURRICULUM VITAE

A.

Personal profile

Full name

Siti Rahayu Binti Shahri

National IC number

910618-14-6478

Birth date

18th June 1991

Citizenship

Malaysian

Place of birth

Kuala Lumpur, Malaysia

Gender

Females

Correspondence address

Batu 2 Kampung Bukit

Badong, 45600 Btg Berjuntai,
Selangor.

Telephone number (HP)

013-2848236

Email address

sitirahayushahri@yahoo.com

B.

Hobbies and interests

I enjoying reading, travelling and exploring places. I like to listen to music and I
enjoying making friend with people. I am fluent in Bahasa Malaysia, good in English
and basic in Mandarin.

41

C.

Education background

1.

Sept 2011- July 2014 : University Technology Mara, Shah Alam

Bachelor of Science (Hons) of Applied Chemistry

2.

2009-2011

: Matriculation College of Negeri Sembilan

Life Science

3.

2007-2008

: Sekolah Menengah Kebangsaan Raja Muda Musa,

Selangor Sijil Pelajaran Malaysia (SPM)

D.

Work experiences

Post

Place

Year

Industrial training

Department of Chemistry

2013

Malaysia, Petaling Jaya

E.

Related experiences

Post

Club

Year

Member

Outward Bound Kesatria

2011-2013

(Uitm Shah Alam)

Member

Applied Chemistry
Society (ACES)

42

2011-2014