Kurdistan Iraqi Region

Ministry of Higher Education

University of Sulaimani
College of Science
Physics Department

Optical Properties
of Polyvinyl - chloride
Alumina Composite
Prepared by
Aso Abu-Baker Husain Samira Ali Faraj
Bakhtear Rasul Sulaiman

Supervised by
Dr. Omed Ghareb Abdullah

2009 – 2010
 Dedication

 Dedicated to our family especially our

faithful fathers and mothers.
 Dedicated to our teachers in physics
department.
 Dedicated to all our best friends.
 Dedicated to University of Sulaimani.

ii
 Acknowledgement

 Praise to God that afford us to complete this

work.

 Thanks for physics Department that let us to

perform this study.

 Thanks to our instructor Dr. Omed Ghareb

who supervised the current study and
guided us loyally.

 Thanks to all our friends and teachers who

helped us.

Aso, Samira and Bakhtear

iii
 Contents

Chapter One: Polymer Structure.

1.1 Introduction…………………………………………………………. 1
1.2 Polymerization Reaction………………………………………….… 2
1.2.1 Chain-Reaction (addition) Polymerization……………………. 2
1.2.2 Step-Reaction (Condensation) Polymerization……………...… 5
1.3 Polymer Chemical Structure………………………………………… 6
1.4 Polymer Physical Structure……………………………………..…… 7
1.5 Classification of Polymers……………………………………..……. 8

Chapter Two: Theoretical Background.

2.1 Introduction ……………..………………………………………… 10

2.2 Band Theory ……………………………………………..……...… 10
2.3 Density of State ……………………………………..…………….. 12
2.4 Band Structure of Crystalline and Amorphous Material ………..… 13
2.5 Optical Properties of Polymers …………………...………..……… 16
2.6 Refractive Index (n) …...………………………………..…………. 17
2.7 Dielectric Polarization………………………………..……………. 18
2.7.1 Atomic Polarization………………………..……………….. 19
2.7.2. Dipolar Polarization…………………..………………….... 20
2.7.3. Ionic Polarization…………………..……………………… 20
2.8 Dielectric Dispersion…………………...………………………….. 21

Chapter Three: Optical Properties.

3.1 Introduction ………………………..……………...………………. 22

3.2 Absorption Coefficient ….……..………………………………….. 23
3.3 The Optical Energy Gap…………………………………..……….. 25
3.4 Optical Absorption …………...………………………..………….. 26
3.5 Optical Properties of Thin Film …….……………..…………….... 28
3.6 Absorption Edge ……..………………………...………………….. 30
3.7 Optical Constants of Thin Films …………….…………………….. 32

iv
Chapter four: results and conclusion.

4.1 Introduction ……………………………..………………………… 34

4.2 Experimental detail …………………..…………………………… 34
4.3 The Absorbance…………………………………………………… 35
4.4 The Transmittance Spectra ………………………...……………… 35
4.5 The Reflectance Spectra ………………………...………………… 36
4.6 Refractive Index ……………………………..….………………… 37
4.7 Extinction Coefficient …………………………….…..….…...…… 38
4.8 Dielectric Constants …………………………………………..…… 39
4.9 The Optical Energy Gap ……………………………………..….… 40
4.10 Width of the tail of localized states ……………………………… 43
4.11 Conclusion…………………………………………….….….…… 45

References …………………………………………………………….. 46

Appendix ………………………………………………………………. 48

v
 Abstract

The study of optical absorption has been one of the most productive
methods in understanding the band structure and energy gap of both
crystalline and amorphous materials. It was well known when the light
incident on a material, the optical phenomena of absorption, reflection and
transmission are observed, the optical absorption constitutes the most
important information to determining the band structures, direct and indirect
transitions, and absorption edge of amorphous and crystalline materials which
illustrated the transition of electron between conduction and valence band.
The measurement of optical absorption coefficient, particularly near the
fundamental absorption edge, is a standard method for the investigation of
optically induced electronic transitions.
The optical properties of prepared Polyvinyl-chloride (PVC) films with
difference filling levels of Alumina were studied in the visible and ultraviolet
wavelength regions. It was found that the optical absorption is due to direct-
allowed transitions, and the energy gaps decrease with increasing Alumina
content for all transitions, while the width of the tail localized states increase
with increasing Alumina content.
All the other optical constants Transmittance, Reflectance, refractive
index 𝑛𝑛, extinction coefficient 𝑘𝑘, the complex dielectric constant have been
also calculated. The dielectric constant increased in the composite samples as
compared with the pure PVC sample prepared by the same method.

vi
 Chapter One
Polymer Structure

1.1 Introduction:
Over half a century ago, Wilhelm Ostwald (1914) coined the phrase “the
land of neglected dimensions” to describe the range of sizes between
molecular and microscopic within which occur most colloidal particle. The
term “neglected dimensions” might have been applied equally well to the
work of polymer molecules, the high-molecular-weight compounds so
important to man and his modern technology. It was not until the 1930’s that
the science of high polymers began to emerge, and the major growth of the
technology of these materials came even later. Yet today polymer dimensions
are neglected no more, for industries associated with polymeric materials
employ more than half of all American chemists and chemical engineers.
A polymer is a large molecule built up by the repetition of small, simple
chemical units. In some cases the repetition is linear, much as a chain is built
up from it is links. In other cases the chains are branched or interconnected to
form three-dimensional networks. The repeat unit of the polymer is usually
equivalent or nearly equivalent to the monomer, or starting material from
which the polymer is formed.
The length of the polymers chain is specified by the number of repeat
units in the chain. This is called the degree of polymerization (DP). The
molecular weight of the polymer is the product of the molecular weight of the
repeat unit and the degree of polymerization. Using poly(vinyl chloride) as an
example, a polymer of degree of polymerization 1000 has a molecular weight
of 63 * 1000 = 63000. Most high polymer useful for plastics, rubbers, or
fibers have molecular weights between 10 000 and 1000 000.

1
 Gradually the study of polymer properties began. Almost all were first
called anomalous because they were so different from the properties of low-
molecular- weight compounds. It was soon realized, however, that polymer
molecules are many times larger than those of ordinary substance. The
presumably anomalous properties of polymers were shown to be normal for
such materials, as the consequences of their size were included in the
theoretical treatments of their properties.
Primary chemical bonds along polymer chains are entirely satisfied. The
only forces between molecules are secondary bond forces of attraction, which
are week relative to primary bond forces. The high molecular weight of
polymer allows these forces to build up enough to impart excellent strength,
dimensional stability, and other mechanical properties to the substances.

1.2 Polymerization Reactions:

The chemical reaction in which high molecular mass molecules are
formed from monomers is known as polymerization.
There are two basic types of polymerization: chain-reaction (or addition)
and step-reaction (or condensation) polymerization.

1.2.1 Chain-Reaction (addition) Polymerization:

One of the most common types of polymer reactions is chain-reaction
(addition) polymerization. This type of polymerization is a three step process
involving two chemical entities. The first, known simply as a monomer, can
be regarded as one link in a polymer chain. It initially exists as simple units.
In nearly all cases, the monomers have at least one carbon-carbon double
bond. Ethylene is one example of a monomer used to make a common
polymer.

2
The other chemical reactant is a catalyst. In chain-reaction polymerization, the
catalyst can be a free-radical peroxide added in relatively low concentrations.
A free-radical is a chemical component that contains a free electron that forms
a covalent bond with an electron on another molecule. The formation of a free
radical from an organic peroxide is shown below:

In this chemical reaction, two free radicals have been formed from the one
molecule of R 2 O 2 . Now that all the chemical components have been
identified, we can begin to look at the polymerization process.

Step 1: Initiation
The first step in the chain-reaction polymerization process, initiation,
occurs when the free-radical catalyst reacts with a double bonded carbon
monomer, beginning the polymer chain. The double carbon bond breaks
apart, the monomer bonds to the free radical, and the free electron is
transferred to the outside carbon atom in this reaction.

Step 2: Propagation
The next step in the process, propagation, is a repetitive operation in
which the physical chain of the polymer is formed. The double bond of
successive monomers is opened up when the monomer is reacted to the

3
reactive polymer chain. The free electron is successively passed down the line
of the chain to the outside carbon atom.

This reaction is able to occur continuously because the energy in the chemical
system is lowered as the chain grows. Thermodynamically speaking, the sum
of the energies of the polymer is less than the sum of the energies of the
individual monomers. Simply put, the single bounds in the polymeric chain
are more stable than the double bonds of the monomer.

Step 3: Termination
Termination occurs when another free radical (R-O.), left over from the
original splitting of the organic peroxide, meets the end of the growing chain.
This free-radical terminates the chain by linking with the last CH 2 . component
of the polymer chain. This reaction produces a complete polymer chain.
Termination can also occur when two unfinished chains bond together. Both
termination types are diagrammed below. Other types of termination are also
possible.

4
 This exothermic reaction occurs extremely fast, forming individual chains
of polyethylene often in less than 0.1 second. The polymers created have
relatively high molecular weights. It is not unusual for branches or cross-links
with other chains to occur along the main chain.

1.2.2 Step-Reaction (condensation) Polymerization:

Step-reaction (condensation) polymerization is another common type of
polymerization. This polymerization method typically produces polymers of
lower molecular weight than chain reactions and requires higher temperatures
to occur. Unlike addition polymerization, step-wise reactions involve two
different types of di-functional monomers or end groups that react with one
another, forming a chain. Condensation polymerization also produces a small
molecular by-product (water, HCl, etc.). Below is an example of the
formation of Nylon 66, a common polymeric clothing material, involving one
each of two monomers, hexamethylene diamine and adipic acid, reacting to
form a dimer of Nylon 66.

At this point, the polymer could grow in either direction by bonding to

another molecule of hexamethylene diamine or adipic acid, or to another
dimer. As the chain grows, the short chain molecules are called oligomers.
This reaction process can, theoretically, continue until no further monomers
and reactive end groups are available. The process, however, is relatively
slow and can take up to several hours or days. Typically this process breeds
5
linear chains that are strung out without any cross-linking or branching, unless
a tri-functional monomer is added.

1.3 Polymer Chemical Structure:

The monomers in a polymer can be arranged in a number of different
ways. As indicated above, both addition and condensation polymers can be
linear, branched, or cross-linked. Linear polymers are made up of one long
continuous chain, without any excess appendages or attachments. Branched
polymers have a chain structure that consists of one main chain of molecules
with smaller molecular chains branching from it. A branched chain-structure
tends to lower the degree of crystallinity and density of a polymer. Cross-
linking in polymers occurs when primary valence bonds are formed between
separate polymer chain molecules.
Chains with only one type of monomer are known as homopolymers. If
two or more different type monomers are involved, the resulting copolymer
can have several configurations or arrangements of the monomers along the
chain. The four main configurations are depicted in Figure (1.1):

Figure (1.1): Rrandom, alternating, block and graft Copolymers

configurations.

A: Random copolymers: The repeating units are arranged randomly on the

chain molecule.

6
 B: Alternating copolymers: There is an ordered (alternating) arrangement of
the two repeating units along the polymer chain.
C: Block copolymers: The chain consists of relatively long sequences
(blocks) of each repeating unit chemically bound together.
D: Graft copolymers: Sequences of one monomer (repeating unit) are
“grafted” onto a backbone of another monomer.

1.4 Polymer Physical Structure:

Segments of polymer molecules can exist in two distinct physical
structures. They can be found in either crystalline or amorphous forms.
Crystalline polymers are only possible if there is a regular chemical structure
(e.g., homopolymers or alternating copolymers), and the chains possess a
highly ordered arrangement of their segments. Crystallinity in polymers is
favored in symmetrical polymer chains, however, it is never 100%. These
semi-crystalline polymers possess a rather typical liquefaction pathway,
retaining their solid state until they reach their melting point at T m .
Amorphous polymers do not show order. The molecular segments in
amorphous polymers or the amorphous domains of semi-crystalline polymers
are randomly arranged and entangled. Amorphous polymers do not have a
definable T m due to their randomness. At low temperatures, below their glass
transition temperature (T g ), the segments are immobile and the sample is
often brittle. As temperatures increase close to T g , the molecular segments can
begin to move. Above T g , the mobility is sufficient (if no crystals are present)
that the polymer can flow as a highly viscous liquid. The viscosity decreases
with increasing temperature and decreasing molecular weight.
In cooling an amorphous material from the liquid state, there is no abrupt
change in volume such as occurs in the case of the cooling of a crystalline
material through its freezing point, 𝑇𝑇𝑓𝑓 . Instead, at the glass transition
temperature, there is a change in the slope of the curve of specific volume
versus temperature, moving from low value in the rubbery state over a range

7
of temperature. This comparison between a crystalline material (1) and an
amorphous material (2) is illustrated in Figure (1.8).

Figure (1.2): Specific Volume versus Temperature graph.

1.5 Classification of Polymers:

Polymers may be classified as follows, according to the mechanical
response at elevated temperatures:
1. Thermoplasts
2. Thermosets

1- Thermoplasts:
Thermoplast polymers soften when heated and harden when cooled.
Simultaneous application of heat and pressure is required to fabricate these
materials. On the molecular level, when the temperature is raised, secondary
bonding forces are diminished so that the relative movement of adjacent
chains is facilitated when a stress is applied.
Most Linear polymers and those having branched structures with flexible
chains are thermoplastics. The commercial available thermoplasts are:
Polyvinyl Chloride (PVC) and Polystyrene, Polymethyl methacrylate, and
Polystyrene.

8
2- Thermosets:
Thermosetting polymers become soft during their first heating and
become permanently hard when cooled. They do not soften during subsequent
heating. Hence, they cannot be remolded (reshaped) by subsequent heating. In
thermosets, during the initial heating, covalent cross-links are formed between
adjacent molecular chain. These bonds anchor the chains together to resist the
vibration and rotational chain motions at high temperatures. Cross linking is
usually extensive in that 10 to 15% of the chains per units are cross linked.
Only heating to excessive temperatures will cause severance of these
crosslink bonds and polymer degradation.
Thermoset polymers are harder, stronger, more brittle than thermoplastics
and have better dimensional stability, and they are more usable in processes
requiring high temperatures.
Most of the cross linked and network polymers which include, Vulcanized
rubbers, Epoxies, Phenolic, Polyester resins, are thermosetting.
Thermosets cannot be recycle, do not melt, are usable at higher
temperatures than thermoplastics, and are more chemically inert.

9
 Chapter Two
Theoretical Background

2.1 Introduction:
When light is incident on a materials, the optical phenomena of
absorption, reflection, and transmission are observed. From these optical
effects, we obtain much of the information. From absorption spectrum as a
function of photon energy, a number of processes can be contributed to
absorption. At high energies photons are absorbed by the transitions of
electrons from filled valence band states to empty conduction band states.
For energies just below the lowest forbidden energy gap, radiation is
absorbed due to the formation of excitants, and electron transitions between
band and impurity states. The transitions of free carriers within energy bands
produce an absorption continuum which increases with decreasing photon
energy. Also, the crystalline lattice itself can absorb radiation, with the energy
being given off in optical phonons. Finally, at low energies, or long
wavelengths, electronic transitions can be observed between impurities and
their associated bands.

2.2 Band theory:

Band theory is a part of solid state physics that examines the behavior of
the electrons in solids. It postulates the existence of energy bands, continuous
ranges of energy values which electrons may or may not occupy.
Band theory is used to explain why different substances have varying
degrees of electrical resistance. The electrons of a single free-standing atom
occupy atomic orbitals, which form a discrete set of energy levels. According
to molecular orbital theory, if several atoms are brought together into a
molecule, their atomic orbitals split, producing a number of molecular orbitals
proportional to the number of atoms. When a large number of atoms (of

10
order 1020 or more) are brought together to form a solid, the number of
orbitals becomes exceedingly large, and the difference in energy between
them becomes very small. However, some intervals of energy contain no
orbitals, no matter how many atoms are aggregated.
Any solid has a large number of bands. In theory, it can be said to have
infinitely many bands (just as an atom has infinitely many energy levels).
Many models have been constructed to try to explain the origin and behavior
of bands. These include:
1- The nearly-free electron model, a modification of the free electron model.
2- The Kronig-Penney mode.
Bands have different widths, based upon the properties of the atomic
orbitals from which they arise. Also, allowed bands may overlap, producing
(for practical purposes) a single large band. While the density of energy states
in a band is very great, it is not uniform. It approaches zero at the band
boundaries, and is generally greatest near the middle of a band. Not all of
these states are occupied by electrons ("filled") at any time. The likelihood of
any particular state being filled at any temperature is given by the Fermi-
Dirac statistics.
The probability is given by the following:
1
𝑓𝑓(𝐸𝐸 ) = 𝐸𝐸−𝐸𝐸𝑓𝑓 (2.1)
1+ 𝑒𝑒 𝐾𝐾𝐾𝐾
where:
𝐾𝐾 is Boltzmann's constant,
𝑇𝑇 is the temperature,
𝐸𝐸𝑓𝑓 is the Fermi energy (or 'Fermi level').
Regardless of the temperature, 𝑓𝑓�𝐸𝐸𝑓𝑓 � = 1/2 , at 𝑇𝑇 = 0, the distribution is
4T

a simple step function:

1 𝑖𝑖𝑖𝑖 0 < 𝐸𝐸 ≤ 𝐸𝐸𝑓𝑓
𝑓𝑓(𝐸𝐸 ) = � (2.2)
0 𝑖𝑖𝑖𝑖 𝐸𝐸𝑓𝑓 < 𝐸𝐸

11
 At non zero temperatures, the step "smooth’s out", so that an appreciable
number of states below the Fermi level are empty, and some states above the
Fermi level are filled. As shown in figure (2.1).

Figure(2.1): Distribution function at three temperatures in Fermi-Dirac

statistics.

2.3 Density of State:

Density of state can be defined as the density of energy levels per unit
energy interval. Density of state (DOS) is a property in statistical
and condensed matter physics that quantifies how closely packed energy
levels are in some physical system. It is often expressed as a function 𝒈𝒈(𝑬𝑬) of
the internal energy 𝑬𝑬, or a function 𝒈𝒈(𝒌𝒌) of the wavevector 𝒌𝒌. It is usually
used with electronic energy levels in a solid. In 3-dimensions, for example,
the density of states in reciprocal space (𝒌𝒌 -space) is:
0T

𝑽𝑽 𝟐𝟐
𝒈𝒈(𝒌𝒌) = 𝒌𝒌 𝒅𝒅𝒅𝒅 (𝟐𝟐. 𝟑𝟑)
𝟐𝟐𝝅𝝅𝟐𝟐
where 𝑽𝑽 is the volume of the solid. A more precise definition is as;
𝒈𝒈(𝑬𝑬)𝒅𝒅𝒅𝒅 is the number of allowed energy levels per unit volume of the
material, within the energy range 𝑬𝑬 𝒕𝒕𝒕𝒕 𝑬𝑬 + 𝒅𝒅𝒅𝒅 (and equivalently for 𝒌𝒌).
To find the density of energy states, the relation between energy and
momentum for a particular particle is used, to express 𝑘𝑘 and 𝑑𝑑𝑑𝑑 in 𝑔𝑔(𝑘𝑘 )𝑑𝑑𝑑𝑑, in
terms of 𝐸𝐸 and 𝑑𝑑𝑑𝑑. For example for a free electron:

12
 𝑝𝑝2 (ℏ𝑘𝑘 )2 ℏ𝑘𝑘
𝐸𝐸 = = ⇛ 𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 (2.4)
2𝑚𝑚 2𝑚𝑚 𝑚𝑚
This gives a density of states at energy 𝐸𝐸 per unit volume,
𝑘𝑘
𝑑𝑑 ∫0 𝑑𝑑3 𝑘𝑘 𝑑𝑑𝑑𝑑
𝑔𝑔(𝐸𝐸 ) = � � (2.5)
𝑑𝑑𝑑𝑑 (𝜕𝜕𝜕𝜕 )3 𝑑𝑑𝑑𝑑

2.4 Band structure of Crystalline and Amorphous material:

The crystalline state can be distinguished from the existence of the long-
range order in three dimensions or from the arrangement of atomic structure,
in crystalline material the atomic structure repeat itself in a periodical way.
The crystal has a band contain a huge number of energy levels equal to
the number of atoms; therefore the band energy appears as a continuous
spectrum. If the atom in crystal becomes close to neighboring atom, each
energy level will split into two level and if the atoms get closer up to distance
equal to the atomic equilibrium distance for lattice, the energy level will split
into two well separated bands, as in the figure (2.2):
Electron
Energy

Conduction
Band

Eg

Valence
Band

 Lattice Spacing

Figure (2.2): The energy band formation.

The distance between the two bands is called the forbidden gap. There are
no energy levels in the forbidden gap or (energy gap). The two splitted bands

13
called the valence and conduction band. The electrons in valence band have a
possibility of moving to the conduction band if they have a chance to get
energy equal or more than the energy gap.
The band energy can be divided to two sub-band, the extended band
which is related to long range order and the charge carrier have a possibility
of moving in a certain path through the material. The charge carrier in this
band can move by hopping only. The space of energy between extended
conduction band and extended valence band called the mobility gap as
illustrated in figure (2.3).

Figure (2.3): Energy (𝐸𝐸) verse Density of state 𝑔𝑔(𝐸𝐸) diagram for crystalline
materials.

It should be noted that the local energy gap (the separation between the
top of the valence band and the bottom of the conduction band) is everywhere
maintained constant. But the density-of-states distribution, which integrates
the number of states at each energy inside the whole volume shows that there
are conduction band states at relatively low potentials and valence band states
in high-potential regions.
The density of states of amorphous is not nil at the band gap of the
material, due to existence of the band tails, i.e., a perturbation of the
conduction and valence bands by the formation of tails of states extending the

14
bands into the energy gap. Since impurities are distributed randomly in the
host crystal, the local interaction will be more or less strong depending on the
local crowding of impurities, as illustrated in figure (2.4).

Figure (2.4): The left diagram shows the perturbation of the band edges by
Coulomb interaction with inhomogeneously distributed impurities. This leads
to the formation of tails of states shown on the right side. The dashed lines
show the distribution of states in the unperturbed case.

In figure (2.4), the region of extended state originated from the

crystallization structure of material. The charge carriers in this region are free
to move. The tall state region is originated from the disordering, dangling
bonds, impurities and defects. Therefore the density of localized tail state
proportion with the increase in disordering, while the extended state of
conduction and valence inversely proportion with disordering.
It has been noted that the absorption edge curves of many amorphous
solids exhibit similar shapes. The absorption edge of such materials can be
recognized by three major regions, shown in figure (2.5).

15
Figure (2.5): An absorption spectrum of amorphous solids consisting of three
major regions of interest.

The behavior in region A arises directly from defect states transitions. The
absorption edge extending in regions A and B is rather complicated and
contains defect-induced tail at the lowest energies, an exponential region at
intermediate energies, and a power-law at the highest energies. The high
absorption coefficient in region A is caused by the transitions between the
extended states. This is then followed by an exponential region B, which
extends over 4 orders of magnitude of the absorption coefficient.
It has been suggested by Tauc that the exponential absorption edge in
interband absorption arises from the electronic transitions between the
localized states in the band edge tails. The density of these localized states is
assumed to fall off with energy, giving rise to the exponential absorption edge
characteristics.

2.5 Optical Properties of Polymers:

The optical properties of polymer depend basically on the reaction
happening between the polymers charge and the electromagnetic field rays.
Therefore, it must be understood that the nature of these charges (ionic,

16
electronic) and their distribution may be bonded as in semiconductors and
insulators may be free as in metals.
The study of optical properties of polymer requires the introduction of
bonds nature and the type of internal structure.
Good optical properties, especially in bulk materials, need a detailed
Knowledge of polymer structure, Generally speaking most of polymers are in
a non-crystalline state. This makes them suffer the softness and cracks. This is
in turn constitutes one of their disadvantages in much application.
However stopping the growth of mer unit can prevent the crystalline.
This will overcome the afro mentioned disadvantages, specifically, this
will produce a thin film of hard surface which provides the strength and
transmittance requirements at the same time.

2.6 Refractive Index (𝒏𝒏):

The speed of the light in the vacuum is constant. However, in other
medium it is inversely proportional to the density of the medium. The ratio of
the light speed in vacuum to the light speed in medium is known as the
refractive index of the medium, which is represented by the symbol (𝑛𝑛).
The electrical component of the incident electromagnetic wave in a
material is work to drift different charge from their original place and produce
dipole moment.
If the frequency of the alternating electric components of electromagnetic
wave is (𝜐𝜐), then the electrical polarization of atoms will oscillate in the same
frequency, and a part of electromagnetic energy will be converts to oscillating
energy for creating dipoles, causing a decrease in the amplitude of the
incident wave.
That loss in energy causes a little dipole oscillates, i.e. the interaction of
charges with electromagnetic wave doesn’t cause losses in energy but
produces recombination of radiation state. The material becomes transmitter

17
for this radiated wave. However, the lack in recombination decreases the light
speed. Then it can be said that the material has (𝑛𝑛) which is given by:
𝑐𝑐
𝑛𝑛 = (2.6)
v
Where 𝑐𝑐 is the velocity of light in vacuum, and v is the velocity of light in
medium. Obviously, the polarization in material is caused by incident
electromagnetic wave and its measured of (𝑛𝑛). Therefore, as the polarization
increases the lacking increases, and also whenever the light velocity is
decreased (𝑛𝑛) is increased too. In other words, it can be said that any
increment in the dipoles density of the material will result in an increment in
refractive index (𝑛𝑛).

2.7 Dielectric Polarization:

One main goal of studies of dielectric polarization is to relate macroscopic
properties such as the dielectric constant to microscopic properties such as the
polarizability.
Dielectric polarization arises from the electrical response of individual
molecules of a medium and may be classified as electronic, atomic,
orientation, and space-charge or interfacial polarization, according to the
mechanism involved.
Electronic polarization represents the distortion of the electron
distribution or motion about the nuclei in an electric field.
Atomic polarization arises from the change in dipole moment
accompanying the stretching of chemical bonds between unlike atoms in
molecules.
Orientation polarization is caused by the partial alignment of polar
molecules, that is, molecules possessing permanent dipole moments, in an
electric field. This mechanism leads to a temperature-dependent component of
polarization at lower frequencies.

18
 Space-charge or interfacial polarization occurs when charge carriers are
present which can migrate an appreciable distance through a dielectric but
which become trapped or cannot discharge at an electrode. This process
always results in a distortion of the macroscopic field and is important only at
low frequencies.

2.7.1 Atomic Polarization:

In the classical approach to the dielectric model, a material is made up of
atoms. Each atom consists of a cloud of negative charge bound to and
surrounding a positive point charge at its center. Because of the comparatively
huge distance between them, none of the atoms in the dielectric material
interact with one another. In the presence of an electric field the charge cloud
is distorted, as shown in the figure (2.6).

Figure (2.6): Schematic to illustrate the atomic polarization.

This can be reduced to a simple dipole using the superposition principle. A

dipole is characterized by its dipole moment, a vector quantity shown in the
figure as the blue arrow labeled M. It is the relationship between the electric
field and the dipole moment that gives rise to the behavior of the dielectric.
When the electric field is removed the atom returns to its original state. The
time required to do so is the so-called relaxation time; an exponential decay.

19
 The relationship between the electric field 𝐸𝐸 and the dipole moment 𝑀𝑀
gives rise to the behavior of the dielectric, which, for a given material, can be
characterized by the function 𝐹𝐹 defined by the equation:
𝑀𝑀 = 𝐹𝐹 (𝐸𝐸 ) (2.7)
When both the type of electric field and the type of material have been
defined, one then chooses the simplest function 𝐹𝐹 that correctly predicts the
phenomena of interest.

2.7.2. Dipolar Polarization:

Dipolar polarization is a polarization that is particular to polar molecules.
This polarization results from permanent dipoles, which retain polarization in
the absence of an external electric field. The assembly of these dipoles forms
a macroscopic polarization.
When an external electric field is applied, the distance between charges,
which is related to chemical bonding, remains constant in the polarization;
however, the polarization itself rotates. Because this rotation completes not
instantaneously but in the delay time 𝜏𝜏, which depends on the torque and the
surrounding local viscosity of the molecules, dipolar polarizations lose the
response to electric fields at the lowest frequency in polarizations. The delay
of the response to the change of the electric field causes friction and heat.

2.7.3 Ionic Polarization:

Ionic polarization is polarization which is caused by relative
displacements between positive and negative ions in ionic crystals.
If crystals or molecules do not consist of only atoms of the same kind, the
distribution of charges around an atom in the crystals or molecules leans to
positive or negative. As a result, when lattice vibrations or molecular
vibrations induce relative displacements of the atoms, the centers of positive
and negative charges might be in different locations. These center positions
are affected by the symmetry of the displacements. When the centers don't

20
correspond, polarizations arise in molecules or crystals. This polarization is
called ionic polarization.

2.8 Dielectric Dispersion:

In physics, dielectric dispersion is the dependence of the permittivity of a
dielectric material on the frequency of an applied electric field. Because there
is always a lag between changes in polarization and changes in an electric
field, the permittivity of the dielectric is a complicated, complex-valued
function of frequency of the electric field. It is very important for the
application of dielectric materials and the analysis of polarization systems.
This is one instance of a general phenomenon known as material
dispersion: a frequency-dependent response of a medium for wave
propagation.
When the frequency becomes higher:
1- it becomes impossible for dipolar polarization to follow the electric
field in the microwave region around 1010 Hz;
2. in the infrared or far-infrared region around 1013 Hz, ionic polarization
loses the response to the electric field;
3- electronic polarization loses its response in the ultraviolet region
around 1015 Hz.
In the wavelength region below ultraviolet, permittivity approaches the
constant ε 0 in every substance, where ε 0 is the permittivity of the free space.
Because permittivity indicates the strength of the relation between an electric
field and polarization, if a polarization process loses its response, permittivity
decreases.

21
 Chapter Three
Optical Properties

3.1 Introduction:
Optical absorption analysis has widely proven to be an important and
efficient tool in exploring and interpreting the various phenomena of
electronic structures and processes in the materials subjected to radiation. The
considerable theoretical investigations on the optical behavior of thin films
deal primarily with optical reflection, transmission, and adsorption properties,
and their relation to the optical constants of films. The importance of studying
the optical properties of a material is offered by the ability of this technique to
provide information regarding the fundamental gap, electronic transition,
trapping levels, and localized states. In general, films are amorphous, and at
most they are polycrystalline in nature.
Over the last decades, advances have been made in understanding the
problem of how the disorder in amorphous materials influences the band
structure and hence the electrical and optical properties of the material.
Optical absorption in solids occurs by various mechanisms, in all of which
the photon energy is absorbed by either the lattice or by electrons, where the
transferred energy is conserved. The lattice (or phonon) absorption gives
information about the atomic vibrations involved. This absorption of radiation
normally occurs in the infrared region of the spectrum. Higher energy parts
could provide information associated with the interband electronic transition.
In these processes, the electrons are excited from the filled band to an empty
band by the photon absorption, and, as a consequence of this, a sharp increase
in the absorption coefficient will result.

22
3.2 Absorption Coefficient:
The absorption coefficient determines how far into a material light of a
particular wavelength can penetrate before it is absorbed. In a material with a
low absorption coefficient, light is only poorly absorbed, and if the material is
thin enough, it will appear transparent to that wavelength. The absorption
coefficient depends on the material and also on the wavelength of light which
is being absorbed. Semiconductor materials have a sharp edge in their
absorption coefficient, since light which has energy below the band gap does
not have sufficient energy to raise an electron across the band gap,
consequently this light is not absorbed.
The appearance of high band in certain range of the absorption spectrum
means the absorbance of a high amount of energy. That is, this amount of
energy, which has been absorbed, is high. This is caused by the transfer
(jump) of a number of molecules from lower energy to a higher one.
However, when a little number of molecules is transferred the total
absorbed energy will be less than the previous case and produce a lower band.
These notes are the basic fundamentals of Beer-Lambert law. The
absorbed parts of incident radiation are directly proportional to the number of
absorbed molecules in the radiation direction.
The Amount of absorbed and transmuted wave in any material is
exponentially proportional to the distance passed through the material (𝑑𝑑) and
the absorption coefficient (𝛼𝛼) It can be calculated from Lambert law as
follows:
𝐼𝐼 = 𝐼𝐼𝑜𝑜 exp(−𝛼𝛼𝛼𝛼 ) (3.1)
Where,
𝐼𝐼𝑜𝑜 : incident light intensity,
𝐼𝐼 : transmitted light intensity,
𝑑𝑑 : substrate thickness, and
𝛼𝛼 : absorption coefficient.

23
 The ratio 𝐼𝐼/𝐼𝐼𝑜𝑜 known as the transmittance (𝑇𝑇) and 𝑙𝑙𝑙𝑙𝑙𝑙 (𝐼𝐼𝑜𝑜 /𝐼𝐼) as the
absorbance (𝐴𝐴). Therefore,
𝐴𝐴 = 𝑙𝑙𝑙𝑙𝑙𝑙 (𝐼𝐼𝑜𝑜 /𝐼𝐼) = −𝑙𝑙𝑙𝑙𝑙𝑙 (𝑇𝑇) (3.2)
The absorption coefficient per unit length 𝛼𝛼 is, related to the extinction
coefficient, 𝑘𝑘, by the following formula:
4𝜋𝜋𝑘𝑘
𝛼𝛼 = (3.3)
𝜆𝜆
Optical absorption and luminescence occur by transition of electrons and
holes between electronic states (bands, tail states, gap states). If electron-
phonon coupling is strong enough self-trapping occurs.
It is well known that an electron is transferred from the valence band to the
conduction band if sufficient energy (basically the gap energy) is provided to
the semiconductor. If the energy is delivered by incident photons the process
is called optical absorption. A number of different phenomena may be
associated with the incidence of light on a material. Figure (3.1) shows a
schematic of the optical absorption spectrum vs. energy of the photons. For
our discussion here, phenomena related to (2) excitons, (3) fundamental
absorption processes and (4) impurities are of interest.

Figure (3.1): Different types of optical absorption phenomena; (1) transitions of

high-lying bands, (2) excitons, (3) fundamental absorption (valence-band-to-
conduction-band transition and Urbach-tail), (4) impurity absorption, (5) free-
carrier absorption and (6) Reststrahlen absorption.

24
3.2 The Optical Energy Gap:
The optical energy gap 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 is another important quantity that
characterizes semiconductors and dielectric materials since it has a paramount
importance in the design and modeling of such materials. The general theory
and many of the experimental results on amorphous semiconductors have
been summarized by Mott and Davis. They show that one feature of such
materials is some sort of energy band structure, but show also that the
normally sharp cutoff in the density of states curves at the band edges is
replaced by a tailing into the normally forbidden energy gap .Thus we expect
a difference in the absorption spectra, particularly at the fundamental
absorption edge, between samples of the same basic material but for which
one is crystalline and the other amorphous.
From the stand point of electron motion a mobility or pseudo gap is
defined and is larger for amorphous materials than for crystals having the
same chemical compositions. The equivalent gaps from the optical stand point
will depend on the form of excitation process taking place in the material
when photons are absorbed. Thus a variety of possibilities will arise,
depending on whether the transitions involved are direct or indirect.
The theory of such transitions has been presented by Davis and Mott and
they take account of the localized electronic states in the mobility or pseudo-
gap. In amorphous materials the k-conservation rule breaks down and thus k is
not a good quantum number .If we assume that the matrix element for optical
transitions has the same value whether or not the initial and final states are
localized, and also that the densities of states at the band edges are linear
functions of the energy, then we may deduce 𝛼𝛼. The equation for optical
absorption coefficient 𝛼𝛼 at a given angular frequency 𝜔𝜔 then reduces to the
form:
2
𝐴𝐴�ℎ𝑣𝑣 − 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 �
𝛼𝛼 (𝜔𝜔) = (3.4)
ℎ𝑣𝑣

25
 where:
𝐴𝐴 = (4𝜋𝜋/𝑐𝑐)𝜎𝜎𝑜𝑜 /𝑛𝑛𝑜𝑜 ∆𝐸𝐸 (3.5)

And where 𝜎𝜎𝑜𝑜 is the electrical conductivity at absolute zero, ∆𝐸𝐸 the width
of the tail of localized states in the normally forbidden band gap, 𝑛𝑛𝑜𝑜 the
refractive index and 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 the optical energy gap.
Thus the optical energy gap may be determined from the extrapolation to
(𝛼𝛼ℎ𝑣𝑣)1/2 = 0 of a plot of (𝛼𝛼ℎ𝑣𝑣)1/2 v. (ℎ𝑣𝑣). Such a theory describes optical
absorption associated with forbidden indirect transitions.

3.3 Optical Absorption:

The energy gap in a material is responsible for the fundamental optical
absorption edge. The fundamental absorption process is one in which a
photon is absorbed and an electron is excited from an occupied valence band
state to an unoccupied conduction band state. If the photon energy (ℎ𝑣𝑣) is less
than the gap energy, such processes are impossible and the photon will not be
absorbed. That is, the material is transparent to electromagnetic radiation for
which (ℎ𝑣𝑣 < 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ). For (ℎ𝑣𝑣 > 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ) on the other hand, such inter band
absorption processes are possible. In high quality crystalline material at low
temperatures, the density of states rises sharply at the band edge and
consequently the absorption rises very rapidly when the photon energy
reaches the gap energy.
Now considering an inter band electronic transition, we see that such
transitions must be essentially vertical on the band diagram. This is required if
the process is to conserve momentum.
This condition is readily satisfied if the maximum of the VB and the
minimum of the CB occur at the same k-value (often k = 0 as in the figure
(3.1) below). If the band structure has this feature, the gap is said to be direct.
Such semiconductors are very useful for electro-optical applications.

26
 Figure (3.1): Direct optical transition.

While in the case the VB maximum and CB maximum do not occur at the
same k-value, the gap is said to be an indirect gap, as shown in figure (3.2).
Absorption over the band gap cannot conserve energy and momentum without
the participation of another particle, usually a phonon. The process then
corresponds to photon → conduction electron plus phonon.
Energy conservation requires ℎ𝑣𝑣 = 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 + ℎ𝑉𝑉 where 𝑉𝑉 is the frequency
of the phonon created in the process. Indirect absorption processes are
possible (after all they satisfy the necessary conservation conditions), but
because of the participation of a third particle (the phonon), their transition
probabilities are much lower than those of direct processes. This kind of
absorption process is illustrated in the diagram below.

27
 Figure (3.2): Indirect optical transitions.

3.5 Optical Properties of Thin Film:

Optical measurement constitutes the most important means of determining
the band structures of materials. Photo induced transitions can occur between
different bands, which lead to the determination of the energy band gap, or
within a single band such as the free carrier absorption. Optical measurements
can also be used to study lattice vibrations.
The transmission coefficient T and the reflection coefficient R are the two
important quantities generally measured. For normal incidence they are given
by:
(1 − 𝑅𝑅 2 ) 𝑒𝑒𝑒𝑒𝑒𝑒(−4𝜋𝜋𝜋𝜋/𝜆𝜆)
𝑇𝑇 = (3.6)
1 − 𝑅𝑅2 exp⁡ (−8𝜋𝜋𝜋𝜋/𝜆𝜆)
(1 − 𝑛𝑛)2 + 𝑘𝑘 2
𝑇𝑇 = (3.7)
(1 + 𝑛𝑛)2 + 𝑘𝑘 2
Where, 𝜆𝜆 is the wave length, 𝑛𝑛 the refractive index, 𝑘𝑘 the absorption
constant, and 𝑥𝑥 the thickness of the sample.
A more realistic view of the energy band structure is displayed in figure
(3.3), where the valence and conduction bands are nonsymmetric. In addition,

28
the conduction band may have more than one minimum, and the valence band
may also have more than one maximum.
Near the absorption edge the absorption coefficient can be expressed as:
𝛾𝛾
𝛼𝛼 ∝ �ℎ𝑣𝑣 − 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 � (3.8)
Where (ℎ𝑣𝑣) is the photon energy, (𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ) is the band gap, and 𝛾𝛾 is a
constant. In the one electron approximation 𝛾𝛾 equals 12 and 32 for allowed direct
transitions and forbidden direct transitions, respectively 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑘𝑘𝑚𝑚𝑚𝑚𝑚𝑚 as
transitions (a) and (b) shown in figure (3.3); the constant 𝛾𝛾 equals 2 for
indirect transitions [transition (c) shown in figure (3.3)], where photons are
involved. In addition, 𝛾𝛾 equals 3 for allowed indirect transitions to exciton
states, where an exciton is a bound electron-hole pair with energy levels in the
band gap and moves through the crystal lattice as a unit.

Figure (3.3): Types of electron transition resulting by optical absorption:

(a) Allowed direct transition, (b) Forbidden direct transition
(c) Allowed indirect transition, (d) Forbidden indirect transition

Near the absorption edge, where the values of (ℎ𝑣𝑣 − 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ) become
comparable with the binding of an exciton, the coulomb interaction between
the free hole and electron must be into account. For (ℎ𝑣𝑣 ≤ 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ) the

29
absorption merges continuously into the absorption caused by the higher
excited states of the exciton. When (ℎ𝑣𝑣 ≫ 𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔 ), higher energy bands
participate in the transition processes, and complicated band structures are
reflected in the absorption coefficient.

3.6 Absorption edge:

The study of optical absorption and particularly the absorption edge is a
useful method for the investigation of optically induced transitions and for the
provision of information about the band structure and energy gap in both
crystalline semiconductors and non-crystalline materials. The principle of this
technique is that a photon with energies greater than the band gap energy will
be absorbed. The absorption edge in many disordered materials follows the
Urbach rule given by:
ℎ𝑣𝑣
𝛼𝛼 (𝑣𝑣 ) = 𝛼𝛼𝑜𝑜 exp � � (3.9)
∆𝐸𝐸
Where 𝛼𝛼(𝑣𝑣) is the absorption coefficient at a frequency of 𝑣𝑣, and ∆𝐸𝐸 is
the width of the tail of localized states in the band gap.
There are two kinds of optical transition at the fundamental edge of
crystalline and non-crystalline semiconductors, direct transitions and indirect
transition, both of which involve the interaction of an electro-magnetic wave
with an electron in the valance band, which is then raised across the
fundamental gap to the conduction band. For the direct optical transition from
the valence band to the conduction band it is essential that the wave vector for
the electron be unchanged. In the case of indirect transition the interactions
with lattice vibrations (phonons) take place; thus the wave vector of the
electron can change in the optical transition and the momentum change will
be taken or given up by phonons. In other words, if the minimum of the
conduction band lies in a different part of 𝑘𝑘-space from the maximum of the
valence band, a direct optical transition from the top of the valence band to
the bottom of the conduction band is forbidden.

30
 Mott and Davis suggested the following expression for direct transitions:
𝑛𝑛
𝛼𝛼 (𝑣𝑣 ) = 𝐵𝐵�ℎ𝑣𝑣 − 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 � /ℎ𝑣𝑣 (3.10)
Where ℎ𝑣𝑣 is incident photon energy, and exponent 𝑛𝑛 can take 0.5 or 1.5
for allowed and forbidden direct transitions respectively, 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 the optical
energy gap, and 𝐵𝐵 is a constant nearly independent on photon energy:
4𝜋𝜋𝜎𝜎𝑜𝑜
𝐵𝐵 = (3.11)
𝑐𝑐𝑛𝑛𝑜𝑜 ∆𝐸𝐸
Where 𝜎𝜎𝑜𝑜 is the electrical conductivity at absolute zero, ∆𝐸𝐸 the width of
the tail of localized states in the normally forbidden band gap, and 𝑛𝑛𝑜𝑜 is the
refractive index.
The following expression is suggested for indirect transitions:
𝑛𝑛
𝛼𝛼 (𝑣𝑣 ) = 𝐵𝐵�ℎ𝑣𝑣 − 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 ± 𝐸𝐸𝑝𝑝ℎ � /ℎ𝑣𝑣 (3.12)
Where 𝐸𝐸𝑝𝑝ℎ is the photon energy and the value of exponent 𝑛𝑛 take the
values 2 and 3 for allowed and forbidden indirect transitions, see figure (3.4).
Thus, this model suggests that a plot of (𝛼𝛼ℎ𝑣𝑣 )1/𝑛𝑛 as a function of (ℎ𝑣𝑣)
should be linear, when this procedure is used, from the zero absorption
extrapolatied value of (ℎ𝑣𝑣) the value of optical gap can be calculated.

Figure (3.4): Allowed and forbidden indirect transformation.

31
3.7 Optical Constants of Thin Films:
The optical properties of a sprayed film depend strongly on the technique
of spray. Two of the most important optical properties are the refractive index
𝑛𝑛 and the extinction coefficient 𝑘𝑘, which are generally called optical
constants.
The theory of the optical absorption gives the relationship between the
absorption coefficient 𝛼𝛼 and the photon energy ℎ𝑣𝑣, for direct allowed
transition as mentioned before.
Using the fundamental relations of photon transmittance 𝑇𝑇 and
absorbance 𝐴𝐴,
𝐼𝐼𝑑𝑑 = 𝐼𝐼𝑜𝑜 𝑒𝑒 −𝛼𝛼𝛼𝛼 (3.13)
Where 𝐼𝐼𝑑𝑑 is the incident photon energy at thickness (𝑑𝑑) inside the
material, and 𝐼𝐼𝑜𝑜 is incident photon energy at surface of material and
𝐼𝐼𝑜𝑜
𝐴𝐴 = 𝑙𝑙𝑙𝑙𝑙𝑙 � � (3.14)
𝐼𝐼𝑑𝑑
We have:
𝐴𝐴
𝛼𝛼 = 2.303 � � (3.15)
𝑑𝑑
The reflectance (𝑅𝑅) has been found by using the relationship:
𝑅𝑅 + 𝑇𝑇 + 𝐴𝐴 = 1 (3.16)
For normal reflectance, we have:
(𝑛𝑛 − 1)2
𝑅𝑅 = (3.17)
(𝑛𝑛 + 1)2
By using the above relation, the refractive index can be determined from
the relation:
(1 + √𝑅𝑅)
𝑛𝑛 = (3.18)
(1 − √𝑅𝑅)
The extinction coefficient is related to the absorption coefficient 𝛼𝛼 by the
relation:
𝛼𝛼𝛼𝛼
𝑘𝑘 = (3.19)
4𝜋𝜋

32
 Where 𝜆𝜆 is the incident photon wavelength.
The real and imaginary parts of dielectric constant (𝜀𝜀𝑟𝑟 and 𝜀𝜀𝑖𝑖 respectively)
can be calculated as follows:
Complex refractive index:
𝑁𝑁 ∗ = 𝑛𝑛 − 𝑖𝑖𝑖𝑖 (3.20)
Complex dielectric constant:
𝜀𝜀 ∗ = 𝜀𝜀𝑟𝑟 − 𝑖𝑖 𝜀𝜀𝑖𝑖 (3.21)
From the relation 𝑁𝑁 ∗ = √𝜀𝜀 ∗ , there fore:
(𝑛𝑛 − 𝑖𝑖𝑖𝑖)2 = 𝜀𝜀𝑟𝑟 − 𝑖𝑖 𝜀𝜀𝑖𝑖 (3.22)
So that:
𝜀𝜀𝑟𝑟 = 𝑛𝑛2 − 𝑘𝑘 2 (3.23)
𝜀𝜀𝑖𝑖 = 2𝑛𝑛𝑛𝑛 (3.24)

33
 Chapter four
Results and Conclusions

4.1 Introduction:
The study of the optical properties of materials is a huge field, this study was
attempted to touch on some of the most basic parts by considering the essential
properties such as absorption, reflection, transmission and refraction.
When white light strikes the surface of the materials, it may be scattered,
reflected, refracted, transmitted or absorbed. Light scattering and reflecting are
surface phenomena, while refracting, transmitting and absorbing are internal
affairs. With regard to surface phenomenon, if the surface is irregular, then the
light is reflected and scattered in all directions. Although the scattering and
reflecting of light is dependent upon the surface finish.
This chapter describe the discussion of results which were getting during
determination of optical properties of prepared films by casting technique with
different concentrations.

4.2 Experimental detail:

Films of PVC - Alumina composite were prepared by solution casting: 4 𝑔𝑔𝑔𝑔
of pure Polyvinyl-chloride (PVC ) supplied from Sigma-Aldrich company has
been dissolved in 20𝑚𝑚𝑚𝑚 of Tetrahydrofuran (THF) to obtain a pure PVC film,
then the same amount of PVC was dissolved with 0.5, 1,2, 𝑎𝑎𝑎𝑎𝑎𝑎 3 𝑔𝑔𝑔𝑔 of Alumina
to prepare the different filling levels of the PVC - Alumina composites, the
complete dissolution was obtained using a magnetic stirrer at room temperature
for 3hr, these homogeneous solutions were spread on a glass plate and allowed
to evaporate the solvent slowly in air at room temperature for 24ℎ. The thickness
of the films was in the range of (0.5 − 0.9)𝑚𝑚𝑚𝑚, it was determined using

34
micrometer at different places in each film and an average was taken. The
thickness of the PVC - Alumina composites are tabulated in table (4.1):

Table(4.1): Thickness of the PVC - Alumina composites:

PVC (gm) Tetra hydrofurain (ml) Al 2 O 3 (gm) Thickness (cm)
4 20 0 0.0785
4 20 0.5 0.052
4 20 1 0.094
4 20 2 0.0545
4 20 3 0.078

4.3 The Absorbance:

The absorbance spectra for PVC - Alumina composite films, having different
concentration, are shown in figure (4.1) these spectra indicate that the films have
low absorbance in the visible and near infrared regions. However, the absorbance
in the near ultraviolet region is high.

0.45
0.4
0.35
0.3
0.25
A

PVC
0.2
PVC-0.5 Al2O3
0.15
PVC-1 Al2O3
0.1
PVC-2 Al2O3
0.05
PVC-3 Al2O3
0
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.1): The optical absorbance of PVC film polymer with difference
concentration of Al 2 O 3 . R R R R

35
4.4 The Transmittance Spectra:
The optical transmittance spectra for PVC - Alumina composite films, having
different concentration, are shown in figure (4.2). All the films demonstrate that
grate transmittance occurs at wavelengths longer than 360nm. Below this value
there is a sharp fall in transmittance of the films, this because of its high energy
gap value which renders strong absorbance of the films in this region. It is
observed that the overall transmittance decreases with the increase of Alumina
concentration. This is due to the overall increase in the absorbance with the
increase of Alumina contents.

0.85 PVC
PVC-0.5 Al2O3
Transmission

0.75 PVC-1 Al2O3

PVC-2 Al2O3
0.65
PVC-3 Al2O3
0.55

0.45

0.35
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.2): Transmission spectrum of PVC film polymer with difference

concentration of Al 2 O 3 .

4.5 The Reflectance Spectra:

The reflectance of PVC - Alumina composite films, was calculated from
equation (3.16). The reflectance spectra represent the interference between the
rays that are reflected from the film faces. Figure (4.3) shows the optical
reflectance spectra for PVC - Alumina composite films. The overall reflectance
of the film increases with the increase Alumina concentrations.

36
 0.25

0.2

Reflection
0.15
PVC

0.1 PVC-0.5 Al2O3

PVC-1 Al2O3
0.05 PVC-2 Al2O3
PVC-3 Al2O3
0
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.3): The Reflectance spectra for PVC film polymer with difference
concentration of Al 2 O 3 .

4.6 Refractive Index:

The optical behavior of a material is generally utilized to determine its
optical constants [i.e. refractive index (𝑛𝑛), extinction coefficient (𝑘𝑘), real (𝜀𝜀𝑟𝑟 ),
and imaginary (𝜀𝜀𝑖𝑖 ) dielectric constants].
The Refractive index was determined from the reflectance data using
equation (3.18). Figure (4.4) shows the variation in the refractive index with the
incident photon wavelength. The increase of the Alumina concentration causes
an overall increase in the refractive index. The increase is due to the over all
increase in the reflectance with the increase of Alumina contents.

37
 2.7

n (Refrective index)
2.5

2.3
PVC
2.1 PVC-0.5 Al2O3
1.9 PVC-1 Al2O3
PVC-2 Al2O3
1.7
PVC-3 Al2O3
1.5
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.4): The Refractive Index (n) for PVC film polymer with difference
concentration of Al 2 O 3 .

4.7 Extinction Coefficient:

The extinction coefficient was determined by using the equation (3.19), after
calculating the absorption constant from equation (3.15). Figure (4.5) shows the
variation of extinction coefficient with the photon wavelength. The value of
extinction coefficient increases as the Alumina concentration increases.

0.00005
K (absorption Constant)

0.000045
0.00004
0.000035
0.00003
0.000025 PVC
0.00002 PVC-0.5 Al2O3
0.000015 PVC-1 Al2O3
0.00001
PVC-2 Al2O3
0.000005
PVC-3 Al2O3
0
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.5): The Extinction coefficient (k) for PVC film polymer with difference
concentration of Al2O3.

38
4.8 Dielectric Constants:
The real and imaginary parts of the dielectric constant were determined using
equations (3.23) and (3.24) respectively. The illustrated in figures (4.6) and (4.7)
showing the variations of the real and imaginary parts of the dielectric constant
with the incident photon wavelength. The imaginary part represents the
absorption of radiation by free carriers. From figure we can see that the real and
imaginary dielectric constant have the same behavior of refractive and extinction
coefficient respectively.

6
PVC
εr

5
PVC-0.5 Al2O3
4 PVC-1 Al2O3

3 PVC-2 Al2O3
PVC-3 Al2O3
2
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.6): Real dielectric constant (𝜀𝜀𝑟𝑟 ) for PVC film polymer with difference
concentration of Al 2 O 3 .

39
 0.00025

0.0002

εi
0.00015
PVC
0.0001 PVC-0.5 Al2O3
PVC-1 Al2O3
0.00005
PVC-2 Al2O3
PVC-3 Al2O3
0
320 330 340 350 360 370 380 390
Wavelength (nm)

Figure (4.7): imaginary dielectric constant (𝜀𝜀𝑖𝑖 ) for PVC film polymer with
difference concentration of Al 2 O 3 .

4.9 The Optical Energy Gap:

Figure (4.8) shows the variation of (𝛼𝛼ℎ𝑣𝑣 )2 as a function of (ℎ𝑣𝑣 ) for pure
PVC polymer, with different Alumina concentration. This plot indicates allowed
direct transition.
The optical energy gap 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 was estimated from extrapolation of linear
portion of the graph to the photon energy axis. From the figure, it is observed
that the optical energy gap decreases with the increase of Alumina concentration.
This may be due to the possibility of structural defects in the films arisen due to
increase of Alumina concentration, which could give rise to the allowed states
near the conduction band in the bandgap. The values of 𝐸𝐸𝑜𝑜𝑜𝑜𝑜𝑜 for allowed direct
transition for all composition are tabulated in Table (4.2).

40
 3500
PVC
3000
PVC-0.5 Al2O3
(αhv)^2 2500 PVC-1 Al2O3
2000 PVC-2 Al2O3
1500 PVC-3 Al2O3

1000

500

0
2.8 3 3.2 3.4 3.6 3.8
hv(eV)

Figure (4.8): variation of (𝛼𝛼ℎ𝑣𝑣 )2 as a function of (ℎ𝑣𝑣 ) for PVC polymer,

with different Alumina concentration.

Table(4.2): Optical energy gape for allowed direct transitions for all composite.

Samples Optical energy gap (eV)

PVC pure 3.52

PVC-0.5 Al2O3 3.38

PVC-1.0 Al2O3 3.26

PVC-2.0 Al2O3 3.10

PVC-3.0 Al2O3 3.04

In order to investigate the existing of forbidden direct, allowed indirect, and

forbidden indirect transitions, the graphs of (𝛼𝛼ℎ𝑣𝑣 )2/3 , (𝛼𝛼ℎ𝑣𝑣 )1/2 , and (𝛼𝛼ℎ𝑣𝑣 )1/3 ,
as a function of (ℎ𝑣𝑣 ) for PVC polymer, with different Alumina concentration, as
shown in figures (4.9),(4.10), and (4.11) respectively. From these figures one can
simply conclude that this transformation was not available.

41
 16
PVC
14
PVC-0.5 Al2O3
12
PVC-1 Al2O3

(αhv)^2/3
10
PVC-2 Al2O3
8
PVC-3 Al2O3
6
4
2
0
2.8 3 3.2 3.4 3.6 3.8
hv(eV)

Figure (4.9): variation of (𝛼𝛼ℎ𝑣𝑣 )2/3 as a function of (ℎ𝑣𝑣 ) for PVC polymer, with
different Alumina concentration.

8
7
6
(αhv)^1/2

5
PVC
4
PVC-0.5 Al2O3
3
PVC-1 Al2O3
2
PVC-2 Al2O3
1
PVC-3 Al2O3
0
3.2 3.3 3.4 3.5 3.6 3.7 3.8
hv(eV)

Figure (4.10): variation of (𝛼𝛼ℎ𝑣𝑣 )1/2 as a function of (ℎ𝑣𝑣 ) for PVC polymer,
with different Alumina concentration.

42
 4

3.5

3
(αhv)^1/3 PVC
2.5
PVC-0.5 Al2O3
2 PVC-1 Al2O3
PVC-2 Al2O3
1.5
PVC-3 Al2O3
1
3.2 3.3 3.4 3.5 3.6 3.7 3.8
hv(eV)

Figure (4.11): variation of (𝛼𝛼ℎ𝑣𝑣 )1/3 as a function of (ℎ𝑣𝑣 ) for PVC polymer, with
different Alumina concentration.

4.10 Width of the tail of localized states:

Width of the tail of localized states (Urbach energy) inside the forbidden
bands, for all compounds can be found in the exponential region by using
the following relation:
 hv 
α (v ) = α ο exp  (4.1)
 ∆E 
 hv 
ln α (v ) = ln α ο +   (4.2)
 ∆E 
It is obvious when (Inα ) is plot against (hv ) , the inverse of slop will be
the value of tail localized state, as shown in figure (4.12). The values of
Urbach energy ∆E for all composition are tabulated in Table (4.3).

43
 3

2.5

ln(α)
PVC
1.5
PVC-0.5 Al2O3
1 PVC-1 Al2O3
PVC-2 Al2O3
0.5
PVC-3 Al2O3
0
3.2 3.3 3.4 3.5 3.6 3.7 3.8
hv(eV)

Figure (4.12): Tail width of the localized states for PVC film polymer
with difference concentration of Al 2 O 3 .

Table(4.3): width of the tail of localized states for all composites.

Samples Tail width ∆E (eV)

PVC pure 0.2605

PVC-0.5 Al2O3 0.4787

PVC-1.0 Al2O3 0.7358

PVC-2.0 Al2O3 0.8969

PVC-3.0 Al2O3 1.1198

44
4.11 Conclusions:
The following conclusions may be drawn from the results we obtained:

1- Optical studies reveal that these pure PVC film, and composite PVC
films with different concentration of Alumina, have an allowed direct
band gap and it’s observed that the bad gap decrease with increase the
concentration of Alumina.

2- Optical studies show that these films have high absorbance in the
ultraviolet and low visible wavelength regions, and a moderate
absorbance in the near infrared and height visible wavelength regions.
Hence they could be effective to use as a solar radiation absorbers for
solar cell. While, high transmittance properties of these films in the near
infrared and height visible wavelength regions, makes a good material for
thermal control window coating for cold climates and antireflective
coating.

3- The refractive index (𝑛𝑛) increase with increase the Alumina concentration
in the height frequency of visible region, this may be very interest in
manufacturing fiber optic.

4- Increase in Alumina concentration in PVC polymer, lead to more stability

in dielectric constant at height values, through a wide range of frequency.
This behavior may be more benefits in electronic devices.

45
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