Kurdistan Iraqi Region

Ministry of Higher Education

Sulaimani University
College of Science
Physics Department

Optical Properties of
Thin Film
Prepared by
Rnjdar Rauff M.
Ali Bakr Ali

Supervised by
Dr. Omed Gh. Abdullah

2005-2006

1
 Contents
Chapter One: Basic Concepts.
1.1 Introduction.
1.2 The Structure of Solid Material.
1.2.1 Crystalline Materials.
1.2.2 Amorphous Materials.
1.3 Differences between crystalline and amorphous solids
1.4 Classification of Amorphous Materials.
1.5 Thin film.
1.6 Thin film deposition.
1.6.1 Chemical deposition.
1.6.2 Physical deposition.
Chapter Two: Band Structure.
2.1 Introduction.
2.2 Band Theory.
2.3 Density of State.
2.4 Band Structure of Crystalline Materials.
2.5 Band Structure of Amorphous Materials.
2.5.1 The Davis-Mott Model.
2.5.2 The Cohen Fritzchc Ovshinsky Model (CFO).
2.5.3 Marshall-Owen Model.
Chapter Three: Optical properties.
3.1 Introduction.
3.2 Optical properties of amorphous and crystal materials.
3.3 Optical absorption.
3.4 Processes of absorption in semiconductors.
3.5 Optical properties of thin film.
3.6 Absorption Edge.
Chapter four: Calculations.
4.1 Introduction.
4.2 Optical energy for allowed direct transitions.
4.3 Optical energy for forbidden direct transitions.
4.4 Optical energy for allowed indirect transitions.
4.5 Optical energy for forbidden indirect transitions.
4.6 Width of the tail of localized states.

References.
Appendixes.

2
 Chapter One
Basic Concepts

1.1 Introduction:
A crystalline solid exhibits translational invariance so that the atoms arrange
themselves in a regular pattern, with a specific lattice spacing between
neighboring atoms, and the same number of nearest neighbor atoms for each
atom. In the amorphous state the number of neighboring atoms varies, and there
is no regular pattern over long distances, although varying amounts of local order
may be present. The latter description is similar at first glance to a liquid at a
given time, but an amorphous state differs from a liquid in detail. Atoms in the
amorphous state do not move far from their equilibrium sites, whereas in a liquid
such movement is common. If a liquid is cooled instantaneously (quenched), it
will usually go to an amorphous state. In contrast, crystalline states are obtained
by slow cooling, with frequent small heating during the cooling process to
remove fault lines. This process is known as annealing.

1.2 The Structure of Solid material:

Solids can fall into one of two categories; those which possess long-range-
order in the disposition of their atoms, and those which do not. The first type of
material is known as a crystal, while the second is termed an amorphous
material.
That is, in a crystal the sites of atoms are determined simply by repeating
some sub-unit of the crystal at regular intervals to fill all space. Mathematically
we describe a crystal in terms of a regularly arranged set of points whose
distribution throughout space looks identical from any point in the set (the

3
lattice), and a prescription telling us how many atoms of each type to associate
with each point and where they should go in relation to that point (the basis).
For example, the sodium chloride crystal structure is based upon the face
centre cubic lattice in which the lattice points are arranged as if at the corners of
an array of adjoining cubes, but with an additional lattice point at the centre of
each face. The basis then dictates that each lattice site be given two atoms (one
Sodium and one chlorine) separated from each other by a distance equal to half
the cube side length.
Different materials have different underlying lattices and different kinds of
basis. There are an infinite number of possible atomic bases, but symmetry
dictates that there are only 14 possible different types of lattice (in 3D), and that
these can be further categorised into just 7 different types of symmetry. The 14
different lattices are known as Bravais lattices, and the 7 different symmetry
groups are known as the crystal systems.
Crystals are the most widely studied solids from the theoretical point of
view, because we can learn about the behaviour of an entire crystal just by
studying a very small portion (remember, the structure simply repeats itself at
regular intervals). Furthermore, crystals are extremely important in everyday life,
in industry, in science and technology: metals are crystalline, for example. In
recent years, amorphous materials, which are very important in the real world,
have attracted much attention, particularly with regard to their structural,
electrical, optical, and magnetic properties. It is not easy to visualize or illustrate
the geometrical arrangement of atoms in an amorphous solid, so that from the
theoretical point the studies of these materials are much more difficult.

4
1.2.1 Crystalline Materials:
More than 90% of naturally occurring and artificially prepared solids are
crystalline. Minerals, sand, clay, limestone, metals, carbon (diamond and
graphite), salts (NaCl, KCl etc.), all have crystalline structures. A crystal is a
regular, repeating arrangement of atoms or molecules. The majority of solids,
including all metals, adopt a crystalline arrangement because the amount of
stabilization achieved by anchoring interactions between neighboring particles is
at its greatest when the particles adopt regular (rather than random)
arrangements.
In the crystalline arrangement, the particles pack efficiently together to
minimize the total intermolecular energy.

Fig (1-1): Schematic illustration of the difference between

a crystalline and amorphous of SiO2.

5
 Crystal structures may be conveniently specified by describing the
arrangement within the solid of a small representative group of atoms or
molecules, called the ‘unit cell.’ By multiplying identical unit cells in three
directions, the location of all the particles in the crystal is determined.
The simplest crystalline unit cell to picture is the cubic, where the atoms are
lined up in a square, 3D grid. The unit cell is simply a box with an atom at each
corner. Simple cubic crystals are relatively rare, mostly because they tend to
easily distort. However, many crystals form body-centered-cubic (bcc) or face-
centered-cubic (fcc) structures, which are cubic with either an extra atom
centered in the cube or centered in each face of the cube. Most metals form bcc,
fcc or Hexagonal Close Packed (hpc) structures; however, the structure can
change depending on temperature.
Crystalline structure is important because it contributes to the properties of
a material. For example, it is easier for planes of atoms to slide by each other if
those planes are closely packed. Therefore, lattice structures with closely packed
planes allow more plastic deformation than those that are not closely packed.
Additionally, cubic lattice structures allow slippage to occur more easily than
non-cubic lattices. This is because their symmetry provides closely packed
planes in several directions. A face-centered cubic crystal structure will exhibit
more ductility (deform more readily under load before breaking) than a body-
centered cubic structure. The bcc lattice, although cubic, is not closely packed
and forms strong metals.

1.2.2 Amorphous Materials:

An amorphous solid is a solid in which there is no long-range order of the
positions of the atoms. (Solids in which there is long-range atomic order are
called crystalline solids.) Most classes of solid materials can be found or
prepared in an amorphous form.

6
 A solid substance with its atoms held apart at equilibrium spacing, but with
no long-range periodicity in atom location in its structure is an amorphous solid.
Examples of amorphous solids are glass and some types of plastic. They are
sometimes described as super cooled liquids because their molecules are
arranged in a random manner some what as in the liquid state.

1.3 Differences between crystalline and amorphous solids:

Although the heart of the difference between crystalline and amorphous
solids occurs on the atomic level, there are several physical characteristics which
can often indicate one type or the other. Crystalline substances have regular
shapes, and form flat faces when they are cleaved or broken. When they are
heated, crystalline solids melt at a definite temperature (unless they decompose
before melting). The regularity of crystalline solids is due to the arrangement of
structural units into an orderly array or lattice.
The x-ray diffraction pattern for single crystal is regular arranged pattern.
While for amorphous several concentric broad and diffuse rings are obtained, as
shown in figure (1-2).

7
1.4 Classification of Amorphous Materials:
Semiconductors are used in a wide variety of applications. Most practically
useful semiconductors are made from crystalline materials. However, some non-
crystalline materials also have useful semiconducting properties. There are two
classes of amorphous semiconductors most commonly investigated: amorphous
germanium, silicon and carbon with tetrahedral coordination and also amorphous
semiconductors containing one or more of the chalcogenide elements, S, Se or
Te. For tetrahedral amorphous materials, the covalent network is macroscopically
extended in three dimensions. In other words, paths of covalent bonds connect
every atoms with every other atom in a macroscopic sample of the material.
However, some solids are representable by disconnected covalent networks: they
are molecular solids. Molecular solids are characterized by the coexistence of
strong (primarily covalent) and weak (intermolecular, primarily ``van der
Waals’’) forces. The chalcogen crystal materials are notable among the molecular
solids. It is very important to notice that molecular solids are naturally classified
into several distinct categories on the basis of the molecular network
dimensionality

1.5 Thin film:

Thin films are material layers of about 1 µm thickness. Electronic
semiconductor devices and optical coatings are the main applications benefiting
from thin film construction. Some work is being done with ferromagnetic thin
films as well for use as computer memory. Ceramic thin films are also in wide
use. The relatively high hardness and inertness of ceramic materials make this
type of thin coating of interest for protection of substrate materials against
corrosion, oxidation and wear. In particular, the use of such coatings on cutting
tools may extend the life of these items by several orders of magnitude.

8
Appplication of thin film
ms:
• m
microelec tronics-eleectrical coonductors,, electricall barriers, diffusion barriers....
• m
magnetic sensors - sense
s I, B or changees in them
m
• g sensorrs, SAW devices
gas d
• t
tailored m
materials-l
layer veryy thin films to develop
d m
materials with new
w
p
properties
s
• o ti-reflectioon coatings
optics-ant
• c
corrosion protectionn
• w resisstance
wear
Speccial Propeerties of Thin
T Filmss:
Differentt from bullk materiaals, thin fillms may be:
b
• not fully dense
• under strress
• differentt defect strructures frrom bulk
• quasi - tw
wo dimenssional (very thin film
ms)
• strongly influenced by surfaace and intterface efffects
mechanical
This willl change electricaal, magnettic, opticaal, thermaal, and m
propperties.
Typiical steps in makingg thin film
ms:
• Emissionn of particcles from source
s ( heeat, high voltage
v . . .)
• Transporrt of particcles to subbstrate (freee vs. direccted)
• Condenssation of particles
p onn substratee.

Fig (11-3): Simpple mode for

f deposittion a thinn film.

9
1.6 Thin film deposition:
Thin film deposition is any technique for depositing a thin film of material
onto a substrate or onto previously deposited layers. "Thin" is a relative term, but
most deposition techniques allow layer thickness to be controlled within a few
tens of nanometers, and some allow one layer of atoms to be deposited at a time.
Deposition techniques fall into two broad categories, based on whether they are
understood in terms of chemistry, or of physics.

1.6.1 Chemical deposition:

Here, a fluid precursor undergoes a chemical change at a solid surface,
leaving a solid layer. An everyday example is the formation of soot on a cool
object when it is placed inside a flame. Since the fluid surrounds the solid object,
deposition happens on every surface, with little regard to direction; thin films
from chemical deposition techniques tend to be conformal, rather than
directional.
Chemical vapor deposition (CVD) is a chemical process for depositing thin
films of various materials. In a typical CVD process the substrate is exposed to
one or more volatile precursors, which react and/or decompose on the substrate
surface to produce the desired deposit. CVD is widely used in the semiconductor
industry, as part of the semiconductor device fabrication process, to deposit
various films including: polycrystalline, amorphous, and epitaxial silicon, SiO2,
silicon germanium, tungsten, silicon nitride, silicon oxynitride, titanium nitride,
and various high-k dielectrics. The CVD process is also used to produce
synthetic diamonds. A number of forms of CVD are in wide use and are
frequently referenced in the literature.

10
• Atmospheric pressure CVD (APCVD) - CVD processes at atmospheric
pressure.
• Atomic layer CVD (ALCVD) - a CVD process in which two
complementary precursors (eg. Al(CH3)3 and H2O) are alternatively
introduced into the reaction chamber. Typically, one of the precursors will
adsorb onto the substrate surface, but cannot completely decompose without
the second precursor. The precursor adsorbs until it saturates the surface and
further growth cannot occur until the second precursor is introduced. Thus
the film thickness is controlled by the number of precursor cycles rather
than the deposition time as is the case for conventional CVD processes. In
theory ALCVD allows for extremely precise control of film thickness and
uniformity.
• Low-pressure CVD (LPCVD)-CVD processes at subatmospheric pressures.
Reduced pressures tend to reduce unwanted gas phase reactions and
improve film uniformity across the wafer. Most modern CVD process are
either LPCVD or UHVCVD.
• Metal-organic CVD (MOCVD) - CVD processes based on metal-organic
precursors, such as Tantalum Ethoxide, Ta(OC2H5)5, to create TaO.
• Plasma-enhanced CVD (PECVD) - CVD processes that utilize a plasma to
enhance chemical reaction rates of the precursors. PECVD processing
allows deposition at lower temperatures, which is often critical in the
manufacture of semiconductors.
• Rapid thermal CVD (RTCVD) - CVD processes that use heating lamps or
other methods to rapidly heat the wafer substrate. Heating only the substrate
rather than the gas or chamber walls helps reduce unwanted gas phase
reactions that can lead to particle formation.
• Remote plasma-enhanced CVD (RPECVD) - Similar to PECVD except
that the wafer substrate is not directly in the plasma discharge region.

11
 Removing the wafer from the plasma region allows processing temperatures
down to room temperature.
• Ultra-high vacuum CVD (UHVCVD) - CVD processes at very low
pressures, typically in the range of a few to a hundred millitorrs.

1.6.2 Physical deposition:

Physical deposition uses mechanical or thermodynamic means to produce a
thin film of solid. Since most engineering materials are held together by
relatively high energies, and chemical reactions are not used to store these
energies, commercial physical deposition systems tend to require a low-pressure
vapor environment to function properly; most can be classified as physical vapor
deposition. The material to be deposited is placed in an energetic, entropic
environment, so that particles of material escape its surface. The whole system is
kept in a vacuum deposition chamber, to allow the particles to travel as freely as
possible. Since particles tend to follow a straight path, films deposited by
physical means are commonly directional, rather than conformal.
Some examples of physical deposition are given below:

1- Thermal evaporator:
Uses an electric resistance heater to melt the material and raise its vapor
pressure to a useful range. This is done in a high vacuum, both to allow the vapor
to reach the substrate without reacting with or scattering against other gas-phase
atoms in the chamber, and reduce the incorporation of impurities from the
residual gas in the vacuum chamber. Obviously, only materials with a much
higher vapor pressure than the heating element can be deposited without
contamination of the film. The source of vaporized material is usually one of two
types.

12
 The simpler, older type relies on resistive heating of a thin folded strip
(boat) of tungsten, tantalum, or molybdenum by a high direct current. Small
amounts of the coating material are loaded into the boat. A high current (10-100
A) is passed through the boat, which undergoes resistive heating. The coating
material is then vaporized thermally. Because the chamber is at a greatly reduced
pressure, there is a very long mean free path for the free atoms or molecules, and
the heavy vapor is able to reach the moving substrates at the top of the chamber.
Here it condenses back to the solid state, forming a thin, uniform film.
Several problems are associated with thermal evaporation. Some useful
substances can react with the hot boat, which can cause impurities to be
deposited with the layers, changing optical properties. In addition, many
materials, particularly metal oxides, cannot be vaporized this way, because the
material of the boat (tungsten, tantalum, or molybdenum) melts at a lower
temperature. Instead of a layer of zirconium oxide, a layer of tungsten would be
deposited on the substrate.

2- Electron beam evaporator:

Fires a high-energy beam from an electron gun to boil a small spot of
material; since the heating is not uniform, lower vapor pressure materials can be
deposited.

3- Sputtering:
Sputtering is a physical process whereby atoms in a solid target material are
ejected into the gas phase due to bombardment of the material by energetic ions
as shown in figure (1-4). It is commonly used for thin-film deposition, as well as
analytical techniques.

13
 Sputtering is a process used to deposit a very thin film onto a substrate
whilst in a vacuum. A high voltage is passed across low pressure gas to create a
plasma of electrons and ions in a high energy state. The ions hit a target of the
desired coating material and cause atoms from that material to be ejected and
bond with the substrate. Sputtering is largely driven by momentum exchange
between the ions and atoms in the material, due to collisions. The process can be
thought of as atomic billiards, with the ion (cue ball) striking a large cluster of
close-packed atoms (billiard balls). Although the first collision pushes atoms
deeper into the cluster, subsequent collisions between the atoms can result in
some of the atoms near the surface being ejected away from the cluster. The
number of atoms ejected from the surface per incident ion is called the sputter
yield and is an important measure of the efficiency of the sputtering process.
Other things the sputter yield depends on are the energy of the incident ions,
the masses of the ions and target atoms, and the binding energy of atoms in the
solid.
The target can be kept at a relatively low temperature, since the process is
not one of evaporation, making this one of the most flexible deposition
techniques. It is especially useful for compounds or mixtures, where different
components would otherwise tend to evaporate at different rates. The schematic
of sputter deposition are shown in figure (1-5).

14
 Fig (1-4): The impact of an atom or ion on a surface produces sputtering from
the surface as a result of the momentum transfer from the in-coming
particle. Unlike many other vapour phase techniques there is no melting
of the material.

Fig (1-5): Sputter deposition process.

4- Pulsed laser deposition:

Pulsed laser deposition is a thin film deposition technique. It uses a pulsed
laser beam to carry out a process of ablation in order to deposit materials as thin
films. Generally, a high vacuum is necessary for their operation. Pulses of
focused laser light transform the target material directly from solid to plasma; the
resulting plume of plasma is thrown perpendicularly away from the surface by
thermal expansion. As expansion cools the plume, it will revert to a gas, but

15
sufficiently high vacuum will allow momentum to carry this gas to the substrate,
where it condenses to a solid state. Pulsed laser deposition systems work by an
ablation process. Pulses of focused laser light to transform the target material
directly from solid to plasma; this plasma usually reverts to a gas before it
reaches the substrate.

Technique Advantages Disadvantages

Dense films
Sputtering Good uniformity relatively slow
Wide range of inorganic materials

Limited range of materials

Fast
Thermal Evaporation Low density films without
Relatively simple
ion or plasma assist

Fast
e-Beam Evaporation high voltages
Wide range of inorganic materials

Difficult to scale
Gives good control of coating
CVD Often uses hazardous liquids
chemistry
or gases

16
 Chapter Two
Band Structure

2-1 Introduction:
Thin films science and technology plays an important role in the high-tech
industries. Thin film technology has been developed primarily for the need of the
integrated circuit industry. The demand for development of smaller and smaller
devices with higher speed especially in new generation of integrated circuits
requires advanced materials and new processing techniques suitable for future
giga scale integration (GSI) technology. In this regard, physics and technology of
thin films can play an important role to acheive this goal. The production of thin
films for device purposes has been developed over the past 40 years. Thin films
as a two dimensional system are of great importance to many real-world
problems. Their material costs are very small as compared to the corresponding
bulk material and they perform the same function when it comes to surface
processes. Thus, knowledge and determination of the nature, functions and new
properties of thin films can be used for the development of new technologies for
future applications.
Thin film technology is based on three foundations: fabrication,
characterization and applications. Some of the important applications of thin
films are microelectronics, communication, optical electronics, catalysis, and
coating of all kinds, and energy generation and conservation strategies.

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.

17
 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 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).
However, all but a few lie at energies so high that any electron that reaches those
energies escapes from the solid. These bands are usually disregarded.
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:

18
 1
f (E ) = E−E f
− (2.1)
1+ e kT

where:
k iis Boltzmaann's consstant,
T is
i the temp
perature,
EF is the Ferrmi energy
y (or 'Ferm
mi level').
ure, f(EF) = 1 / 2. At T=0, tthe distrib
Regardleess of the temperatu bution is a
simp
ple step fuunction:

(2.2)
At non zero
z peratures, the step "smooths out", so that an ap
temp ppreciablee
num
mber of staates below
w the Ferm
mi level are
a empty
y, and som
me states above thee
Ferm
mi level arre filled. As
A shown in figure ((2-1).

19
2-3 Density
D off state:
c be deefined as the densiity of eneergy levels per unitt
Density of state can
y of state (DOS) is a property
enerrgy intervaal. Density y in statisttical and condensed
c d
mattter physiccs that qu
uantifies how
h closeely packed
d energy levels aree in somee
physsical systeem. It is offten expreessed as a function g(E)
g of thhe internal energy E,
E
or a function g(k) of th
he waveveector k. It is usually
y used witth electron
nic energy
y
leveels in a sollid. In 3-d
dimensionss, for exam
mple, the density
d off states in reciprocal
spacce (k-space) is

(2.3)
where V is the vollume of th
he solid. A more preecise definnition is as; g(E) dE
E
is th
he numberr of allow
wed energy
y levels per unit vo
olume of tthe materiial, within
n
the energy
e ran
nge E to E + dE (an
nd equivaleently for k).
k

20
 To find the denssity of en
nergy stattes, the relation
r beetween en
nergy and
d
mom
mentum foor a particu
ular particcle is usedd, to expresss k and ddk in g(k)d
dk
In terms of E and dE.
d For ex
xample forr a free eleectron:

, (2.4)
This givees a densitty of statees at energgy E per un
nit volumee,

(2.5)
The amoorphous sttate meanss that the chemical band is bbroken as a result in
n
the differencee in length
h and ang
gles of latttice bond
d, thereforre all eneergy levelss
appeears in dennsity of staate diagraam as threee essentiall regions aas in the fiigure:

21
 In figure (2-2b), first region (a) is the extended state which originated from
the crystallization structure of material. The charge carriers in this region is free
to move. The second region (b) is the tall state which originated from the
disordering. The density of localized tail state proportion with the increase in
disordering while the extended state of valence and conduction inversely
proportion with disordering. The last region (c) is the deep state which is
originated from dangling bonds, impurities and defects.
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 in fig (2-2a) above.

2.4 Band structure of crystalline material:

We can distinguish the crystalline state 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 (2-3):

22
 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
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.

2.5 Band structure of amorphous material:

The amorphous semiconductor and insulator are known to have to some
extend the short range order, the disordering reflect itself on density of state
diagram. Energy band in amorphous will be divided to two band, the first one
present the extended state range order. The second one present the tail of
localized state witch can be related to disordering.

23
 The difference between the energy of the extended state conduction band
and the extended state of valance band called the mobility gap. This gap is
unreal, in other words, the amorphous material has no real energy gap because of
the interference of localized states.
There are several models have been proposed and all use the concept of
localized states and mobility gap ,but vary as the extent of the supposed edges of
distributions of localized states and these models are:
1- Davis and Mott model.
2- The Cohen, Fritzsche and Ovshinsky model(C.F.O model).
3- Marshall-Owen Model.

2-5-1 The Davis-Mott model:

The Davis and Mott model based on the idea of making a strong distinction
between localized states. Some of the localized state originates from the lack of
long-range order and others are due to defects in the structure the lack of long-
range order creates localized states extents only to EA and EB in the mobility gap
as in the figure (2-4).
The defects states from longer tails but of insufficient density to pin the
Fermi level .They further proposed the existence of a band of compensated levels
near the middle of the band gap in order to pin the Fermi level.
The center band may split into a donor-acceptor band, as shown in
figure(2-5).

24
Figure (2-4:) Density of state N(E) as a function of energy (E) in an amorphous
semiconductor according to Davis and Mott.

Figure(2-5): Density of state N(E) as a function of energy (E) In an

amorphous semiconductor with acceptor and donor peaks Due to dangling
bonds (modified Davis and mott model).

25
 2.5.2 The Cohen, Fritzsche and Ovshinsky model (C.F.O model):
The amorphous semiconductors alloys are highly disordered so that the tails
of the conduction band and valance band can overlap as in the figure (2-6):

Figure (2-6): Density of state N(E) in an amorphous semiconductor

(C.F.O model).

Cohen pointed that a localized state is always identitiable either as a

valance band tail state or as a conduction band tail state even when its energy lies
in the overlapping region.
Redistribution in the conduction band tail, and which are negatively
charged, and empty states in the valance band tail which are positively charged.

26
2.5.3 Marshall-Owen Model:
Marshall and Owen suggest that the position of the fermi level is
determined by the well separated bands of donors and acceptors in the upper and
lower halves of the mobility gap as shown in figure(2-7)

Figure (2-7): Marshall and Owen model.

27
 Chapter Three
Optical properties

3.1 Introduction:
When light is incident on a semiconductor, 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 there associated bands.
Many of these processes have important technological applications; for
example, intrinsic photo detectors utilize band to band absorption. While
semiconductor Lasers generally operate by means of transitions between
impurity and band states.

3.2 Optical properties of amorphous and crystal 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

28
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 α. The equation for optical
absorption coefficient α at a given angular frequency w then reduces to the form:

α (ω ) = A(hω − Eopt )2 hω (3.1)

where:
A = (4π c )σ ο nο ∆E (3.2)

And where σ ο is the electrical conductivity at absolute zero, ∆E the width

of the tail of localized states in the normally forbidden band gap, nο the

refractive index and Eopt the optical energy gap.

29
 Thus the optical energy gap may be determined from the extrapolation to

(αhω ) 12 = 0 of a plot of (αhω )

1
2
v. (hω ) . Such a theory describes optical
absorption associated with forbidden indirect transitions.
The spectrally transmittances where determined by means of a Perkin-
Elmer spectrophotometer and typical results shown in the figure (3-1):

Figure (3-1):

3.3 Optical absorption:

The energy gap in a semiconductor 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 (hω ) is less

30
than the gap energy, such processes are impossible and the photon will not be
absorbed. That is, the semiconductor is transparent to electromagnetic radiation
( ) ( )
for which hω < E gap . For hω > E gap on the other hand, such inter band
absorption processes are possible (with a qualification that we will discuss
shortly). In high quality semiconductor crystals 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.
Observation of the optical absorption edge is the most common means of
measuring the energy gap in semiconductors.
As an example, consider the semiconductor GaAs commonly used in

electro-optical applications. The band gap energy is (E = 1.4eV ) . This

gap

corresponds to a photon frequency (ω = 2.1× 10 14

Hz ) and a wavelength

(λ ≈ 0.9 × 10 −6
)
m ≈ 900nm . This wavelength lies just outside the visible range
in the very near infrared. This tells us that GaAs is transparent to infrared light,
but is opaque (strongly absorbing) in the visible.
This is true of many common semiconductors because their energy gaps are
of order 1eV or less. There is a complication to the fundamental absorption
process that limits the usefulness of some semiconductors for optical
applications. These include, unfortunately, silicon, the most ubiquitous material
in semiconductor applications. Recall that when we studied the optical phonon
modes, we found that the intersection of the photon’s dispersion relation and that
of the optical modes occurs very close to k = 0. This is because the photon
wavelength λ photon at the relevant frequency is much longer than a typical

inter atomic spacing a , in the crystal lattice. Thus k photon = 2π λ photon is

very small on the scale of the Brillouin zone k BZ = π a .

31
 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: hk photon = h∆k electron .

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 diagram
below). If the band structure has this feature, the gap is said to be direct [see
figure (3-2)].
Such semiconductors are very useful for electro-optical applications.

Figure (3-2): Direct optical transition.

What if the VB maximum and CB maximum do not occur at the same k-

value? In this case the gap is said to be an indirect gap. 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.

32
 Energy conservation requires hω = E gap + hW where W is the frequency
of the phonon created in the process.
To conserve momentum, the phonon must have a wave vector K phonon =
k(CB max) – k(VB min) since k photon ≈  0. 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.

Figure (3-3): Indirect optical transitions.

Despite the inefficiency of electron-hole excitation (interband absorption) in

indirect semiconductors, these materials nevertheless have important
applications. One example is the crystalline silicon solar cell.

33
 Figure (3-4): Comparison between direct and indirect transitions.

3.4 Processes of absorption in semiconductors:

Within these energy level systems we can have a variety of mechanisms by
which electrons (and holes) absorb optical energy. Most of these processes can
occur in quantum wells, wires, and dots, as well as in bulk material:
1- Band-to-band: an electron in the valence band absorbs a photon with enough
energy to be excited to the conduction band, leaving a hole behind.
2- Band-to-exciton: an electron in the valence band absorbs almost enough
energy to be excited to the conduction band. The electron and hole it leaves
behind remain electrically "bound" together, much like the electron and
proton of a hydrogen atom.

34
 3- Band-to-impurity or impurity to band: an electron absorbs a photon that
excites it from the valence band to an empty impurity atom or from an
occupied impurity atom to the conduction band.
4- Free carrier: an electron in the conduction band, or hole in the valence band,
absorbs a photon and is excited to a higher energy level within the same set
of bands (i.e., conduction or valence). In quantum structures there can be
photon absorption due to carriers being excited between the quantum levels
within the same band (termed "intra-band"), as well as between the various
quantum levels in one band and those in another "(inter-band").
5- Intra-band: these transitions can occur only between even and odd index
levels and are only operative for light polarized parallel to the direction of
quantization. That is, in a quantum well the light must be polarized normal
to the well itself, and in the direction of the composition variation.
6- Inter-band: inter-band transitions can occur between conduction and valence
bands, or between different valence bands (light-hole, heavy-hole, and spin-
off). There are transitions can be active for either polarization of the light,
depending on the symmetries of the respective bands.

3.5 Optical properties of thin film:

Optical measurement constitutes the most important means of determining
the band structures of semiconductors. 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:

T=
(1 − R )exp(− 4πx λ )
2

(3.3)
1 − R 2 exp(− 8πx λ )

35
 T=
(1− n) + k2
2

(3.4)
(1 + n )2 + k 2
Where, λ is the wave length, n the refractive index, k the absorption
constant, and x the thickness of the sample.
The absorption coefficient per unit length α is given by:
4πk
α= (3.5)
λ
By analyzing the T − λ or R − λ data at normal incidence, or by making
observations of R or T for different angles of incidence, both n and k can be
obtained and related to transition energy between bands.
Near the absorption edge the absorption coefficient can be expressed as:

α ∝ (hω − E g )γ (3.6)

Where (hω ) is the photon energy, E g ( ) is the band gap, and γ is a

1 3
constant. In the one electron approximation γ equals and for allowed
2 2

direct transitions and forbidden direct transitions, respectively k min = k max as

transitions (a) and (b) shown in figure (3-5); the constant γ equals 2 for indirect
transitions [transition (c) shown in figure (3-5)], where photons are involved. In
addition, γ 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.

36
 Near the absorption edge, where the values of (hω − E )g become
comparable with the binding of an exciton, the coulomb interaction between the
(
free hole and electron must be into account. For hω ≤ E g ) the absorption

merges continuously into the absorption caused by the higher excited states of
( )
the exciton. When hω >> E g , higher energy bands participate in the transition
processes, and complicated band structures are reflected in the absorption
coefficient.

37
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:

⎛ hω ⎞
α (ω ) = α ο exp⎜ ⎟ (3.7)
⎝ ∆E ⎠
Where α (ω ) is the absorption coefficient at an angular frequency of
ω = 2πν , and ∆E 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 k-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.
Mott and Davis suggested the following expression for direct transitions:

α (ω ) = B (hω − Eopt )n hω (3.8)

38
 Where hω is incident photon energy and exponent n can take 0.5 or 1.5

for allowed and forbidden direct transitions respectively, Eopt the optical energy
gap, and:
4πσ ο
B= (3.9)
cnο ∆E

Where σ ο is the electrical conductivity at absolute zero, ∆E the width of

the tail of localized states in the normally forbidden band gap. nο the refractive
index.
The following expression is suggested for indirect transitions:

α (ω ) = B (hω − Eopt ± E ph )n hω (3.10)

Where E ph is the photon energy and the value of exponent n take the
values 2 and 3 for allowed and forbidden indirect transitions, see figure (3-6).

(αhω )
1
Thus, this model suggests that a plot of as a function of hω
n

should be linear, when this procedure is used, from the zero absorption
extrapolatied value of hω the value of optical gap can be calculated.

Figure (3-6): Allowed and forbidden indirect transformation.

39
 Chapter four
Calculations

4.1 Introduction:
For the sake of more understanding and practice our knowledge, the
analyzed was done on the data of absorption coefficient versus photon energy for
thin films of Chromium Oxide (Cr2O3), Cobalt Oxide (Co3O4), and a mixture of
both compounds in different ratio, reported in reference [8]. All the thin films are
prepared by the method of chemical spry pyrolysis deposition on cover glass
substrates at (673 K), with thickness between (225-275 nm).
The spectra were analyzed and the optical energy gap for both, allowed and
forbidden, direct and indirect transition were evaluated for all data. Also the
width of the localized states inside the forbidden gap is investigated in this
chapter, in the calculation the MATLAB software was used as shown in
Appendix.

4.2 Optical energy for allowed direct transitions:

In the allowed direct transitions the conduction electron transfer from
the top of valence bands to the bottom of conduction bands, with
conservation of momentum. In this case the following relation was
suggested:

α (ω ) = B (hω − Eopt ) hω
1
2
(4.1)
One can calculate the energy gap for allowed direct transition by

plotting figure between (αhω ) versus (hω ) , as shown in figure (3.1) to

2

figure (3.5). It is obvious that the extension of this curve will intersection
with (hω ) , which its value is Eopt for this type of transition. The values of

40
Eopt for allowed direct transition for all composition are tabulated in

Table(3.1).

Table(3.1): Optical energy gape for allowed direct transitions for all
component.

Percentage Optical energy

Cr2O3:Co3O4 gap (eV)

100 : 0 3.28

75 : 25 2.67

50 : 50 2.08

25 : 75 1.97

0 : 100 1.92

11 100% Cr2O3
x 10
16

14

12

10
(alfa*hv) 2

0
2.6 2.8 3 3.2 3.4 3.6 3.8 4
hv

Figure (4-1): Optical energy for allowed direct transitions for 100% Cr2O3

41
 11 75% Cr2O3 + 25% Co3O4
x 10
15

10
(alfa*hv) 2

0
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2
hv

Figure (4-2): Optical energy for allowed direct transitions for 75% Cr2O3 :
25% C03O4

11
x 10 50% Cr2O3 + 50% Co3O4
11

10

7
(alfa*hv) 2

1
1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-3): Optical energy for allowed direct transitions for 50% Cr2O3 :
50% C03O4

42
 11
x 10 25% Cr2O3 + 75% Co3O4
11

10

7
(alfa*hv) 2

1
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-4): Optical energy for allowed direct transitions for 25% Cr2O3 :
75% C03O4

11
x 10 100% Co3O4
11

10

7
(alfa*hv) 2

1
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
hv

Figure (4-5): Optical energy for allowed direct transitions for 100% C03O4

43
4.3 Optical energy for forbidden direct transitions:
In the forbidden direct transitions the conduction electron transfer from
valence bands to conduction bands vertically, with conservation of
momentum. In this case the following relation was suggested:

α (ω ) = B (hω − Eopt ) hω
3
2
(4.2)

One can calculate the energy gap of forbidden direct transition by

plotting figure between (αhω ) 3 versus (hω ) , as shown in figure (3.6) to

2

figure (3.10). It is obvious that the extension of this curve will intersection
with (hω ) , which its value is Eopt for this type of transition. The values of

Eopt for forbidden direct transition for all composition are tabulated in

Table (3.2).

Table(3.2): Optical energy gape for forbidden direct transitions for all
component.

Percentage Optical energy

Cr2O3:Co3O4 gap (eV)

100 : 0 2.86

75 : 25 2.47

50 : 50 1.99

25 : 75 1.79

0 : 100 1.73

44
 100% Cr2O3
12000

11000

10000

9000

8000
(alfa*hv) 2/3

7000

6000

5000

4000

3000

2000
2.6 2.8 3 3.2 3.4 3.6 3.8 4
hv

Figure (4-6): Optical energy for forbidden direct transitions for 100% Cr2O3

75% Cr2O3 + 25% Co3O4

12000

11000

10000

9000
(alfa*hv) 2/3

8000

7000

6000

5000

4000
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2
hv

Figure (4-7): Optical energy for forbidden direct transitions for 75% Cr2O3
: 25% C03O4

45
 50% Cr2O3 + 50% Co3O4
11000

10000

9000
(alfa*hv) 2/3

8000

7000

6000

5000
1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-8): Optical energy for forbidden direct transitions for 50% Cr2O3
: 50% C03O4

25% Cr2O3 + 75% Co3O4

11000

10000

9000
(alfa*hv) 2/3

8000

7000

6000

5000
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-9): Optical energy for forbidden direct transitions for 25% Cr2O3
: 75% C03O4

46
 100% Co3O4
10500

10000

9500

9000

8500
(alfa*hv) 2/3

8000

7500

7000

6500

6000

5500
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
hv

Figure (4-10): Optical energy for forbidden direct transitions for 100%
C03O4

4.4 Optical energy for allowed indirect transitions:

In the allowed indirect transitions the conduction electron transfer from
the top of valence bands to the conduction bands not vertically, that is to say
absorption over the band gap cannot conserve energy and momentum
without the participation of another particle, usually a phonon. In this case
the following relation was suggested:

α (ω ) = B (hω − Eopt ± E ph )2 hω (4.3)

The energy gap for allowed indirect transition can be calculated simply

by plotting figure between (αhω ) 2 versus (hω ) , as shown in figure (3.11)

1

to figure (3.15). It is obvious that the extension of this curve will

intersection with (hω ) , which its value is will be (E opt + E ph ) or

47
(E opt − E ph ) for this type of transition; and from these two values Eopt can

be calculated. The values of Eopt for allowed direct transition for all

composition are tabulated in Table (3.3).

Table(3.3): Optical energy gape for allowed indirect transitions for all
component.

Percentage Optical energy

Cr2O3:Co3O4 gap (eV)

100 : 0 2.835

75 : 25 2.450

50 : 50 1.973

25 : 75 1.795

0 : 100 1.785

48
 100% Cr2O3
1200

1100

1000

900
(alfa*hv) 1/2

800

700

600

500

400
2.6 2.8 3 3.2 3.4 3.6 3.8 4
hv

Figure (4-11): Optical energy for allowed indirect transitions for 100% Cr2O3

75% Cr2O3 + 25% Co3O4

1200

1100

1000

900
(alfa*hv) 1/2

800

700

600

500
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2
hv

Figure (4-12): Optical energy for allowed indirect transitions for 75%
Cr2O3 : 25% C03O4

49
 50% Cr2O3 + 50% Co3O4
1050

1000

950

900
(alfa*hv) 1/2

850

800

750

700

650

600
1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-13): Optical energy for allowed indirect transitions for 50%
Cr2O3 : 50% C03O4

25% Cr2O3 + 75% Co3O4

1050

1000

950

900
(alfa*hv) 1/2

850

800

750

700

650

600
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-14): Optical energy for allowed indirect transitions for 25%
Cr2O3 : 75% C03O4

50
 100% Co3O4
1050

1000

950

900
(alfa*hv) 1/2

850

800

750

700

650
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
hv

Figure (4-15): Optical energy for allowed indirect transitions for 100%
C03O4

4.5 Optical energy for forbidden indirect transitions:

In the forbidden indirect transitions the conduction electron transfer
from the valence bands to the conduction bands not vertically, that is to say
absorption over the band gap cannot conserve energy and momentum
without the participation of another particle, usually a phonon. In this case
the following relation was suggested:

α (ω ) = B (hω − Eopt ± E ph )3 hω (4.4)

The energy gap for forbidden indirect transition can be calculated

simply by plotting figure between (αhω )3 versus (hω ) , as shown in figure

1

(3.16) to figure (3.20). It is obvious that the extension of this curve will
intersection with (hω ) , which its value is will be (E opt + E ph ) or

(E opt − E ph ) for this type of transition; and from these two values Eopt can

51
be calculated. The values of Eopt for allowed direct transition for all

composition are tabulated in Table (3.4).

Table(3.4): Optical energy gape for forbidden indirect transitions for all
component.

Percentage Optical energy

Cr2O3:Co3O4 gap (eV)

100 : 0 2.770

75 : 25 2.440

50 : 50 1.950

25 : 75 1.775

0 : 100 1.765

100% Cr2O3
110

100

90
(alfa*hv) 1/3

80

70

60

50
2.6 2.8 3 3.2 3.4 3.6 3.8 4
hv

Figure (4-16): Optical energy for forbidden indirect transitions for 100% Cr2O3

52
 75% Cr2O3 + 25% Co3O4
110

105

100

95
(alfa*hv) 1/3

90

85

80

75

70

65
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2
hv

Figure (4-17): Optical energy for forbidden indirect transitions for 75%
Cr2O3 : 25% C03O4

50% Cr2O3 + 50% Co3O4

105

100

95

90
(alfa*hv) 1/3

85

80

75

70
1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-18): Optical energy for forbidden indirect transitions for 50%
Cr2O3 : 50% C03O4

53
 25% Cr2O3 + 75% Co3O4
105

100

95

90
(alfa*hv) 1/3

85

80

75

70
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-19): Optical energy for forbidden indirect transitions for 25%
Cr2O3 : 75% C03O4

100% Co3O4
105

100

95
(alfa*hv) 1/3

90

85

80

75
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
hv

Figure (4-20): Optical energy for forbidden indirect transitions for 100%
C03O4

54
4.5 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:

⎛ hω ⎞
α (ω ) = α ο exp⎜ ⎟ (4.5)
⎝ ∆E ⎠
⎛ hω ⎞
ln α (ω ) = ln α ο + ⎜ ⎟ (4.6)
⎝ ∆E ⎠
It is obvious when (Inα ) is plot against (hω ) , the inverse of slop will
be the value of tail localized state, as shown in figure (3.21) to figure (3.25).
The values of Urbach energy ∆E for all composition are tabulated in
Table(3.5).

Table(3.5): width of the tail of localized states for all component.

Percentage Tail width ∆E

Cr2O3:Co3O4 (eV)

100 : 0 0.628

75 : 25 0.848

50 : 50 0.566

25 : 75 0.926

0 : 100 0.757

55
 100% Cr2O3
13

12.8

12.6

12.4

12.2
ln (alfa)

12

11.8

11.6

11.4

11.2

11
2.6 2.8 3 3.2 3.4 3.6 3.8 4
hv

Figure (4-21): width of the tail of localized states for 100% Cr2O3
75% Cr2O3 + 25% Co3O4
13

12.8

12.6

12.4
ln (alfa)

12.2

12

11.8

11.6

2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.2
hv

Figure (4-22): width of the tail of localized states for 75% Cr2O3 : 25% C03O4

56
 50% Cr2O3 + 50% Co3O4
13.1

13

12.9

12.8

12.7
ln (alfa)

12.6

12.5

12.4

12.3

12.2

12.1
1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-23): width of the tail of localized states for 50% Cr2O3 : 50% C03O4

25% Cr2O3 + 75% Co3O4

13

12.9

12.8

12.7
ln (alfa)

12.6

12.5

12.4

12.3
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
hv

Figure (4-24): width of the tail of localized states for 25% Cr2O3 : 75% C03O4

57
 100% Co3O4
13.1

13

12.9

12.8
ln (alfa)

12.7

12.6

12.5

12.4
1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3
hv

Figure (4-25): width of the tail of localized states for 100% C03O4

58
 References

[1] M. N. Said, "Studies some of the physical properties of thin films of Barium
Tituate by using Co-Evaporation technique at low pressure", PhD thesis,
Baghdad University, (1996).
[2] David Adler, Brian B. Schwartz, and Martin C. Steele, "Physical properties of
amorphous material", (1988).
[3] M. H. Brodsky, "Amorphous semiconductors", Topics in Applied Physics,
Vol. 36, "Optical properties of amorphous semiconductors", by G. A. N.
Connell, (1979).
[4] C. A. Hogarth, A. A. Hosseini, "Optical absorption near the fundamental
absorption edge in some vanadate glasses", Journal of Materials science 18,
2697-2705, (1983).
[5] C. A. Hogarth and M. N. Khan, "A study of optical absorpition in some
sodium titanium silicate glasses", Journal of Non-Crystalline Solids, 24,
277-282, (1977).
[6] Charles Kittel, “ Introduction to Solid State Physics”, six edition, John Wiley
and Sons, Inc., (1986).
[7] J. S. Blakemore, "Solid state physics", Second Edition, by W. B. Saunders
Company, (1974).
[8] Enas S. Al-Mizban, “A Study of Optical and Electrical Properties of Cr2O3
and Co3O4 Thin Films and Their Mixture”, M.Sc. thesis, Baghdad
University, (1997).
[9] Saz Kamal, Shillan Ali, "Comparing between different types of thin films
preparation methods", fourth class report, University of Sulaimani, (2004).
[10] M. Ashraf Chaudhry, M. Shakeel Bilal, A. R. Kausar and M. Altaf, “Optical
band gap of cadmium phosphate glass containing lanthanum oxide”, Il
Nuovo Cimento, 19, 1, 17-21, (1997).

59
[11] M. Thamilselvan, K. Premnazeer, D. Mangalaraj, Sa. K. Narayandass, and
Junsin Yi, “Influence of density of states on optical properties of GaSe thin
film”, Cryst. Res. Technol. 39, 2, 137-142 (2004).
[12] Y. C. Ratnakaram and A. Viswanadha Reddy, “Correlation of radiative
properties of rare earth ions (Pr3+ and Nd3+) in chlorophosphate glasses-
0.1 and 0.5 mol% concentrations”, Bull. Mater. Sci., 24, 5, 539-545, (2001).

60
 Appendix

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%% Optical Propertes of Thin Film Co2O3-C03O4 %%%%%
%%%%% with deffrent consentration %%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%% 100% Cr2O3 %%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

hv1=[2.7,2.8,2.9,3.0,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8];
alfa1=[0.6,0.7,0.8,1.0,1.3,1.6,1.9,2.2,2.4,2.8,3.1,3.3];
alfa1=alfa1*10^5;
for i=1:12
alfasqwar1(i)=(alfa1(i)*hv1(i))^2;
alfa321(i)=(alfa1(i)*hv1(i))^(2/3);
alfahvroot1(i)=sqrt(alfa1(i)*hv1(i));
alfahv31(i)=(alfa1(i)*hv1(i))^(1/3);
lnalfa1(i)=log(alfa1(i));
end

plot (hv1,alfa1),xlabel('hv'),ylabel('alfa'),title('100% Cr2O3');

pause
%subplot(2,2,1);
plot (hv1,alfasqwar1),xlabel('hv'),ylabel('(alfa*hv) 2'),title('100% Cr2O3');
pause
%subplot(2,2,2);
plot (hv1,alfa321),xlabel('hv'),ylabel('(alfa*hv) 2/3'),title('100% Cr2O3');
pause

61
%subplot(2,2,3);
plot (hv1,alfahvroot1),xlabel('hv'),ylabel('(alfa*hv) 1/2'),title('100% Cr2O3');
pause
%subplot(2,2,4);
plot (hv1,alfahv31),xlabel('hv'),ylabel('(alfa*hv) 1/3'),title('100% Cr2O3');
pause
subplot(1,1,1);
plot (hv1,lnalfa1,'rd'),xlabel('hv'),ylabel('ln (alfa)'),title('100% Cr2O3');
pause

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%% 75% Cr2O3 + 25% Co3O4 %%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

hv2=[2.2,2.3,2.4,2.5,2.7,2.8,3.0,3.1,3.2];
alfa2=[1.3,1.4,1.6,1.7,1.9,2.3,3.1,3.4,3.8];
alfa2=alfa2*10^5;
for i=1:9
alfasqwar2(i)=(alfa2(i)*hv2(i))^2;
alfa322(i)=(alfa2(i)*hv2(i))^(2/3);
alfahvroot2(i)=sqrt(alfa2(i)*hv2(i));
alfahv32(i)=(alfa2(i)*hv2(i))^(1/3);
lnalfa2(i)=log(alfa2(i));
end

subplot(1,1,1);
plot (hv2,alfa2),xlabel('hv'),ylabel('alfa'),title('75% Cr2O3 + 25% Co3O4');
pause
%subplot(2,2,1);
plot (hv2,alfasqwar2),xlabel('hv'),ylabel('(alfa*hv) 2'),title('75% Cr2O3 + 25% Co3O4');
pause
%subplot(2,2,2);
plot (hv2,alfa322),xlabel('hv'),ylabel('(alfa*hv) 2/3'),title('75% Cr2O3 + 25% Co3O4');

62
pause
%subplot(2,2,3);
plot (hv2,alfahvroot2),xlabel('hv'),ylabel('(alfa*hv) 1/2'),title('75% Cr2O3 + 25% Co3O4');
pause
%subplot(2,2,4);
plot (hv2,alfahv32),xlabel('hv'),ylabel('(alfa*hv) 1/3'),title('75% Cr2O3 + 25% Co3O4');
pause
subplot(1,1,1);
plot (hv2,lnalfa2,'rd'),xlabel('hv'),ylabel('ln (alfa)'),title('75% Cr2O3 + 25% Co3O4');
pause

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%% 50% Cr2O3 + 50% Co3O4 %%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

hv3=[1.9,2.0,2.1,2.2,2.3,2.4,2.5];
alfa3=[1.9,2.1,2.7,3.0,3.6,3.9,4.1];
alfa3=alfa3*10^5;
for i=1:7
alfasqwar3(i)=(alfa3(i)*hv3(i))^2;
alfa323(i)=(alfa3(i)*hv3(i))^(2/3);
alfahvroot3(i)=sqrt(alfa3(i)*hv3(i));
alfahv33(i)=(alfa3(i)*hv3(i))^(1/3);
lnalfa3(i)=log(alfa3(i));
end

subplot(1,1,1);
plot (hv3,alfa3),xlabel('hv'),ylabel('alfa'),title('50% Cr2O3 + 50% Co3O4');
pause
%subplot(2,2,1);
plot (hv3,alfasqwar3),xlabel('hv'),ylabel('(alfa*hv) 2'),title('50% Cr2O3 + 50% Co3O4');
pause
%subplot(2,2,2);

63
plot (hv3,alfa323),xlabel('hv'),ylabel('(alfa*hv) 2/3'),title('50% Cr2O3 + 50% Co3O4');
pause
%subplot(2,2,3);
plot (hv3,alfahvroot3),xlabel('hv'),ylabel('(alfa*hv) 1/2'),title('50% Cr2O3 + 50% Co3O4');
pause
%subplot(2,2,4);
plot (hv3,alfahv33),xlabel('hv'),ylabel('(alfa*hv) 1/3'),title('50% Cr2O3 + 50% Co3O4');
pause
subplot(1,1,1);
plot (hv3,lnalfa3,'rd'),xlabel('hv'),ylabel('ln (alfa)'),title('50% Cr2O3 + 50% Co3O4');
pause

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%% 25% Cr2O3 + 75% Co3O4 %%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

hv4=[1.6,1.7,1.95,2.05,2.12,2.2,2.3,2.4];
alfa4=[2.4,2.25,2.6,3.0,3.25,3.5,3.9,4.2];
alfa4=alfa4*10^5;
for i=1:8
alfasqwar4(i)=(alfa4(i)*hv4(i))^2;
alfa324(i)=(alfa4(i)*hv4(i))^(2/3);
alfahvroot4(i)=sqrt(alfa4(i)*hv4(i));
alfahv34(i)=(alfa4(i)*hv4(i))^(1/3);
lnalfa4(i)=log(alfa4(i));
end

subplot(1,1,1);
plot (hv4,alfa4),xlabel('hv'),ylabel('alfa'),title('25% Cr2O3 + 75% Co3O4');
pause
%subplot(2,2,1);
plot (hv4,alfasqwar4),xlabel('hv'),ylabel('(alfa*hv) 2'),title('25% Cr2O3 + 75% Co3O4');
pause

64
%subplot(2,2,2);
plot (hv4,alfa324),xlabel('hv'),ylabel('(alfa*hv) 2/3'),title('25% Cr2O3 + 75% Co3O4');
pause
%subplot(2,2,3);
plot (hv4,alfahvroot4),xlabel('hv'),ylabel('(alfa*hv) 1/2'),title('25% Cr2O3 + 75% Co3O4');
pause
%subplot(2,2,4);
plot (hv4,alfahv34),xlabel('hv'),ylabel('(alfa*hv) 1/3'),title('25% Cr2O3 + 75% Co3O4');
pause
subplot(1,1,1);
plot (hv4,lnalfa4,'rd'),xlabel('hv'),ylabel('ln (alfa)'),title('25% Cr2O3 + 75% Co3O4');
pause

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%% 100% Co3O4 %%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

hv5=[1.51,1.55,1.61,1.7,1.75,1.85,1.92,2.0,2.1,2.17];
alfa5=[2.85,2.8,2.65,2.5,2.6,3.0,3.35,3.75,4.15,4.65];
alfa5=alfa5*10^5;
for i=1:10
alfasqwar5(i)=(alfa5(i)*hv5(i))^2;
alfa325(i)=(alfa5(i)*hv5(i))^(2/3);
alfahvroot5(i)=sqrt(alfa5(i)*hv5(i));
alfahv35(i)=(alfa5(i)*hv5(i))^(1/3);
lnalfa5(i)=log(alfa5(i));
end

subplot(1,1,1);
plot (hv5,alfa5),xlabel('hv'),ylabel('alfa'),title('100% Co3O4');
pause
%subplot(2,2,1);
plot (hv5,alfasqwar5),xlabel('hv'),ylabel('(alfa*hv) 2'),title('100% Co3O4');

65
pause
%subplot(2,2,2);
plot (hv5,alfa325),xlabel('hv'),ylabel('(alfa*hv) 2/3'),title('100% Co3O4');
pause
%subplot(2,2,3);
plot (hv5,alfahvroot5),xlabel('hv'),ylabel('(alfa*hv) 1/2'),title ('100% Co3O4');
pause
%subplot(2,2,4);
plot (hv5,alfahv35),xlabel('hv'),ylabel('(alfa*hv) 1/3'),title('100% Co3O4');
pause
subplot(1,1,1);
plot (hv5,lnalfa5,'rd'),xlabel('hv'),ylabel('ln (alfa)'),title ('100% Co3O4');
pause

end

66