THE OPTICAL AND ELECTRICAL PROPERTIES OF Zn1-xCuxS THIN FILMS

SYNTHESIS, USING CHEMICAL BATH DEPOSITION TECHNIQUE.

BY

SHANGE SUEGA
18/48315/UE

A PROJECT SUBMITTED TO THE

DEPARTMENT OF PHYSICS
COLLEGE OF SCIENCE
FEDERAL UNIVERSITY OF AGRICULTURE, MAKURDI.
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF
BACHELOR OF SCIENCE DEGREE IN BSC PHYSICS.

APRIL, 2021.

i
 DECLARATION

I, shange suega declare that this research project (the optical and electrical properties of Zn 1-

CuxS thin films synthesis using chemical bath deposition technique) is an original work
x

done by me and has not been presented in part or whole to any institution for the award of a

degree or similar certificate.

SHANGE SUEGA
Name of Student

18/48315/UE
Matriculation Number of Student

……………………………………………..
Signature of Student

……………………………………………..
Date

ii
 CERTIFICATION

We, the undersigned, certify that this research project (the optical and electrical properties

of Zn1-xCuxS thin films synthesis using chemical bath deposition technique) presented by

shange suega be accepted as fulfilling part of the requirements for the award of Bachelor of

Science Degree in Bsc physics.

……………………………………. ……………………………..
Dr. I. Ahemen Date
Project Supervisor

……………………………………. ……………………………..
Dr. I. Ahemen Date
Head of Department

……………………………………. …………………………...
External Supervisor Date

iii
 DEDICATION

This work is dedicated to the Sovereign God who has made all things possible for me, to

my aunty and her husband, Mr. and Mrs. Peters Eleche and my big cousin Dr. Louis Eleche,

who has always being my source of motivation, you are heavily appreciated.

iv
 ACKNOWLEDGEMENT

My insufficient and unreserved gratitude goes to the Almighty God for His faithfulness,
love, mercies, grace, guidance and provision that kept and sustained me right from the
beginning of my higher education to the climax culminating in this research project.

My most sincere appreciation goes to my supervisors, Dr. I. Ahemen and Dr. D. Hile, for
their fatherly love, reproof, advice, guidance and understanding, knowing and condoning
my weaknesses, God bless you both abundantly.

I want to as well appreciate the entire lecturers, who not only impacted knowledge unto
me, but instilled discipline, God bless them all richly.

I am indebted to my sweet aunty and her husband Mr. and Mrs PETERS ELECHE for their
immeasurable love, encouragement, financial, spiritual and moral support. my profound
gratitude goes to uncle ALIH ALFA and pastor AYUBA ADAMU for their care, support,
love and encouragement.

I sincerely thank and appreciate my friends and loved ones, Emah victor, Alogah James,
Agada Dorcas, Igomu Ene Blessing, Abah Mathew, Agada Moses, Joseph Garuba Favor
and many others that space and time will not permit me to mention, you are always
remembered.

I sincerely appreciate the Chief Laboratory Technologist, Mr. Julius Nkav, for his
assistance culminating to the success of this research.

Finally, God bless all who have in one way or another supported me.

v
 TABLE OF CONTENTS

Contents Page No

Title page i

Declaration ii

Certification iii

Dedication iv

Acknowledgement v

Abstract vi

Table of content vii

List of tables viii

List of figures ix

CHAPTER ONE

1.0 Introduction 1

1.1 Background of Study 1

1.2 Statement of Problem 2

1.3 Aim and Objectives of Study 2

1.4 significance of the Study 3

1.5 scope of study 4

CHAPTER TWO

2.0 Literature Review 4

vi
2.1 Semiconductors 4

2.2 Classification of semiconductors 5

2.2.1 crystalline semiconductors 5

2.2.2 polycrystalline semiconductor 6

2.2.3 Amorphous semiconductor 6

2.3 Properties of semiconductor 6

2.4 Bandgap 7

2.5 Photoconductive effect 8

2.6 Optical properties of materials 8

2.6.1 Refraction 10

2.6.2 Reflection 12

2.6.3 Absorption 13

2.6.3.1 Absorption mechanism 14

2.6.4 Transmission 14

2.7 Beer Lambert law 14

2.8 Zinc sulfide 16

2.9 Review of related work on ZnS 16

2.10 Thin film 18

2.11 Types of thin film deposition techniques 18

vii
2.11.1 Chemical vapor deposition (CVD) 19

2.11.2 Successive ion layer absorption and reaction (SILAR) method 19

2.11.3 Chemical bath deposition 19

2.11.4 Electrophoretic deposition 20

2.11.15 Sputtering 20

CHAPTER THREE

3.0 Materials and Methods

3.1 Method 21

3.1.1 Substrate Preparation 21

3.1.2 Experiment 22

3.2 Characterization technique 22

3.2.1 Absorption measurement 23

3.2.2 Profilometry 23

3.2.3 Hall Effect Measurement 23

3.3.1 Hall voltage measurement 23

CHAPTER FOUR

4.0 Result, Analysis and Discussion 25

4.1 Optical Absorption 25

viii
4.2 Transmittance 32

4.3 Determination of Optical Bandgap 39

4.4 Profiler 48

4.5 Hall Effect Measurement 48

CHAPTER FIVE

5.0 Conclusion and Recommendation 50

5.1 Conclusion 50

5.2 Recommendation 50

References

ix
 LIST OF TABLES

Table Page Number

1: Materials and their various refractive index 12

2: Absorbance and wavelength of the various deposited films 31

3: Percentage transmittance and wavelength of the various deposited films. 38

4: Variation of energy bandgap with copper concentration using Tauc’s relation. 47

5: Result of Hall Effect Measurement. 49

x
 LIST OF FIGURES

Figure 1: Effect of incident ray on a material 9

Figure 2: Refraction of light ray. 11

Figure 3: Absorbance spectra of ZnS:Cu at 0 M 25

Figure 4: Absorbance spectra of ZnS:Cu at 0.01 M 26

Figure 5: Absorbance spectra of ZnS:Cu at 0.02 M 27

Figure 6: Absorbance spectra of ZnS:Cu at 0.03 M 28

Figure 7: Absorbance spectra of ZnS:Cu at 0.04 M 29

Figure 8: Absorbance spectra of ZnS:Cu at 0.05 M 30

Figure 9: Transmittance spectra of ZnS at 0 M 32

Figure 10: Transmittance spectra of ZnS:Cu at 0.01 M 33

Figure 11: Transmittance spectra of ZnS:Cu at 0.02 M 34

Figure 12: Transmittance spectra of ZnS:Cu at 0.03 M 35

Figure 13: Transmittance spectra of ZnS:Cu at 0.04 M 36

Figure 14: Transmittance spectra of ZnS:Cu at 0.05 M 37

Figure 15: plot of absorbance2 against Energy at 0 M 40

Figure 16: plot of absorbance2 against Energy at 0.01 M 41

xi
Figure 17: plot of absorbance2 against Energy at 0.02 M 42

Figure 18: plot of absorbance2 against Energy at 0.03 M 43

Figure 19: plot of absorbance2 against Energy at 0.04 M 44

Figure 20: plot of absorbance2 against Energy at 0.05 M 45

Figure 21: Diagram of the profile of ZnS. 48

xii
 ABSTRACT

Copper doped Zinc sulfide thin films were prepared from aqueous solution mixture of zinc
acetate dehydrate, copper acetate, thiourea, and sodium tricitrate using triethanolamine as
a complexing agent and ammonia solution was used in controlling the pH of the mixed
solution, using chemical bath deposition method. The experiment was carried out at 353 k,
optimum deposition time lasted for 2 hours using alkaline bath with maintained pH of 10.5
the investigation of the optical properties was carried out using UV- visible
spectrophotometer and the profile of the films was taken in order to determine the thickness
of the films, after which hall effect measurement was carried out to determine whether the
semiconductor is either P-type or N-type. Analysis was made on the deposited thin film, the
optical parameters which include; absorbance, transmittance and the bandgap of both the
doped and undoped ZnS were all analyzed and discussed. High absorbance was seen in the
UV region, which is otherwise to transmittance, meanwhile bandgap tends to increase with
increase in copper concentration. The result showed that Cu doping has effects on the
optical properties of ZnS thin films, and such thin films could be suitable for wide range of
applications in luminescence and optoelectronic devices. .

xiii
 CHAPTER ONE

1.0 INTRODUCTION
1.1 Background of study
Metal chalcogenides are important class of semiconductor materials. A chalcogen is a
chemical compound consisting of at least one chalcogen anion (eg. S, Se, O, Te etc.) and
one or two electropositive element. Although all the elements of group 16 in the periodic
table are defined as chalcogens, the term chalcogenide is more commonly reserved for
sulfides, selenides and tellurides.
The potential applications of chalcogenide based materials in electronic and optoelectronic
devices are vast but have received little attention until recently due to cheap and wide
availability of silicon based alternatives (Tan, 2006). Chalcogenides II-VI compound
semiconductors, such as zinc sulfide (ZnS) has generated a lot of interest among scientists
because of its extensive use in the fabrication of solid state devices such as solar cells, thin
film transistors and electroluminescent displays.
ZnS is an important group II-IV semiconductor with a large direct bandgap of 3.5-3.7 eV in
the UV range (Vin et al., 2008). ZnS is a white to yellow colored powder or crystal with
molecular mass of 97.474 g/mol and density of 4.090 g/m3. It is typically encountered in
the more stable cubic form, known also as zinc blende or sphalerite. The hexagonal form is
also known both as a synthetic material and as the mineral wurtzite, both sphalerite and
wurzite are intrinsic wide bandgap semiconductors. The cubic form has a bandgap of 3.54
eV at 3300 k whereas the hexagonal form has a bandgap of 3.91 eV (wells, 1984). ZnS has
a melting point (phase transition) of 102℃ . The cubic form is stable at room temperature
while the less dense hexagonal form (wurtzite) is stable above 102 ℃ at atmospheric
pressure (Gilbert et al., 2002).
Semiconductor thin films have shown superior luminescence characteristics and hign
quantum efficiency, doped thin films exhibit interesting optoelectronic properties and are
potential candidates for variety of applications. ZnS has been used widely as an important
phosphor for photoluminescence, electroluminescence and cathode luminescence devices
1
due to its better chemical stability compared to other chalcogenides such as ZnSe. Doping
of ZnS thin films by transition metal ions e.g. Mn, Cu, and rare earth ions e.g. Eu have been
successfully done by techniques such as thermal evaporation, sol gel processing, co-
precipitation, micro emulsion etc. These doped ZnS semiconductor materials have a wide
range of applications in electroluminescence devices, phosphors, light emitting displays,
and optical sensors.
ZnS was used by Ernest Rutherford and others in the early days of nuclear physics as a
scintillation detector because it emits light on excitation by x-rays or electron beam, making
it useful for x-ray screen and cathode ray tubes. It also exhibits phosphorescence due to
impurities on illumination with blue or ultraviolet light (Greenwood et al., 1984). ZnS thin
film has been found valuable in various devices.
1.2 Statement of the problem
Though research on ZnS thin film including materials preparation and structural
characterization has been carried out due to its high demand in the solid state devices, there
is need to exploit more especially when the material is doped with appropriate metal to
boast its properties. in this present study, the emphasis is to prepare thin films of zinc
sulfide doped with copper in an alkaline medium and study the optical properties.
1.3Aim and objectives
The main aim of this work is to synthesize and characterize ZnS:Cu, thereby investigating
both the optical and electrical properties of thin film deposited from chemical bath
technique. The objective is:
i. To deposit ZnS:Cu thin film from chemical bath containing zinc acetate
dehydrate, copper(ii) acetate monohydrate, thiourea, urea, hydrazine and
tryethanolamine.
ii. To characterize and study the effect of the dopant concentration on the optical
properties of the thin films.
iii. To determine the mobility of charge carriers.
iv. To determine if the semiconductor is either p-type or n-type semiconductor.

2
1.4 Significance of the study
Effort has been made currently for finding new materials from low cost energy conversion.
Among the materials of recent research are CdS, CdSe, ZnSe, etc. which fall in the group ii-
iv family of compounds (Zainel et al., 1996), due to their photo and electro luminescence
properties and promising applications in optoelectronics. The recent surge of activity in
wide bandgap materials like zinc sulfide doped with copper has arisen from the need for
electronic devices operating at high power levels and high temperatures. Zinc sulfide doped
with copper is an attractive material due to its properties like direct bandgap and
transparency over a wide range of visible spectrum.
1.5 Scope of study
The research will center on the chemical bath deposition method in the preparation and
deposition of thin film on glass substrates, because such processing method is particularly
appropriate for the production of devices for which large area substrates and low cost are
essential, such as solar cells.

3
 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Semiconductors

A semiconductor is a material that has electrical conductivity between a conductor (e.g

aluminum) and an insulator (Yacobi, 2003). Semiconductors have been the subject of very
extensive research over recent decades, not simply because of their intrinsic interest but also
because of their evermore numerous and powerful applications: in rectifiers, transistors,
photoelectric cells, magnetometers, solar cells, reprography, lasers, and so forth. Starting
with the development of the transistor by John Bardeen, Walter Brattain and William
Shockley at Bell Telephone Laboratories in 1947, the technology of semiconductors has
exploded. With the creation of integrated circuits and chips, semiconductor devices have
penetrated into large parts of our lives. The modern desktop or laptop computer would be
unthinkable without microelectronic semiconductor devices, and so would a myriad of other
devices (Peterson and Bailey, 2005). In recent times, the study of semiconductors in the
bulk has been replaced with that of thin films. Involvement with thin films dates to the
metal ages of antiquity. As a modern science, thin films have been prepared ever since
vacuum systems first became available, but deposition as a means of producing films for
device purposes is a development of the past 40 years. Thin metallic film creating on glass
or plastic were among the first to be exploited for optical purposes, ranging from mirrors to
sunglasses and this still continues as a major, typically high vacuum, high through output
business.

Semiconductor thin film technology has attracted much attention, because of its matchless
size dependent properties and applications in the optoelectronic devices, solar cells, sensors
and laser materials. As thin film deposition processes have developed very rapidly over the
past 25 years, particularly on the context of semiconductor devices, processes have become
highly specialized (Ohring, 1992; Venables, 2003). Sulfide thin films such as ZnS have
generated a lot of interest among scientists because of its extensive use in the fabrication of
4
solid state devices. There is diverse range of applications of thin films of this semiconductor
and this is reflected in the large amount of literature available on its properties reported by
various authors using different deposition techniques. In 2008, Ilenikena successfully
produced semiconductor thin films of coper CuS and ZnS on glass microscope slides at 320
k and pH values of 7, 9, 10, 11 and 12 using improved chemical bath deposition method.
The results show that pH increases with the optical and solid state properties (such as
transmittance, energy bandgap, refractive index, absorption coefficient, dielectric constant,
thickness and so on) of the films. Semiconductors are mainly classified into categories
namely, intrinsic semiconductor and extrinsic semiconductor, intrinsic semiconductor
material is chemically very pure and poses poor conductivity; it has equal number of
negative carrier (electron) and positive carrier (hole). An extrinsic semiconductor is an
improved intrinsic semiconductor with a small amount of impurity added by a process
known as doping (Acivisatos, 1996)

2.2 Classification of semiconductor

There are several ways of classifying semiconductor, these include: crystalline,

polycrystalline and amorphous. Each type is characterized by the size of ordered region
within the material. An ordered region is spatial volume in which atoms or molecules have
a regular geometric arrangement or periodicity (Neamen, 2003).

2.2.1 Crystalline Semiconductors

A crystalline material consists of atoms that are arranged in a periodic, regularly repeated
three dimensional pattern in crystalline materials, a radial distribution function exhibit
series of sharp peak indicative of the long-range order. The electronic band structure in
these materials have periodicity of the atomic structure, the presence of long range order
result in a band structure with allowed and forbidden electronic level with sharp band edges
and a fundamental energy gap separating the valence band from the conduction band
(Yacobi, 2003)

5
2.2.2 Polycrystalline Semiconductor

A polycrystalline material consist of crystal grain that are randomly oriented with respect to
each other and between them, two grain boundaries exist. An important parameter is the
grain size and its distribution. Polycrystalline semiconductor are used in cheap large-area
application such as solar cell or thin films transistor, polycrystalline material can be
lubricated from an amorphous material using annealing procedure (Grondman, 2006)

2.2.3 Amorphous Semiconductor

An amorphous solid is any non-crystalline solid in which the atom and molecules are not
organized in a definite lattice pattern structure. It is made such that long range atomic order
is absent. According to Grondman, (2006) amorphous solids, never the less retain the short
range order due to vacancy of atom which is also a characteristic of crystalline solids. The
short-range order is responsible for observation of semiconductor properties such as an
optical absorption edge and also thermally activated conductivity. Amorphous material can
be re-crystallized into polycrystalline material upon annealing. The number of nearest
neighbors to any atom is not much different from the corresponding number in the
crystalline material (Yacobi, 2003)

2.3 Properties of Semiconductor

Semiconductors have number of unique properties. These properties are;

i. Light Emission: in certain semiconductor excited electrons can relax by emitting

light instead of producing heat, these semiconductors are used in the construction of
light emitting diode and florescent quantum dots.
ii. Variation Conductivity: pure semiconductor as a consequence of just having the
full its valence band through techniques such as doping the semiconductor can be
modified to have an excess of electron (becoming an n-type semiconductor) in both

6
 cases, the semiconductor become more conductive (the conductivity can be increased
by one million fold or more). Semiconductor devices exploit this effect to shape
electrical current.
iii. Thermal Energy Conversion: Semi-conductor have large thermoelectric power
factor making them useful in thermo generation and a high thermoelectric figure of
metric, making them useful in the thermoelectric cooker.
iv. Excited Electron: A difference in their electrical properties that would cause it to
have thermal equilibrium and create a non-equilibrium situation. This introduce
electron and holes to the system which interact via a process called bipolar diffusion.
Whenever thermal equilibrium is distributed in a semi-conducting material, the
amount of holes and electron charges. Such disruption can occur as a result of
photons which can enter the system and create electrons and holes. The process that
creates and annihilates electrons and holes are called generation and recombination.
2.4 Bandgap
A bandgap is the distance between the valence band of the electrons and the
conduction band. Essentially, the bandgap represents the minimum energy that is
required to excite an electron up to a state in the conduction band where it can
participate in conduction. The lower energy level is the valence band and thus, if a
gap exists between the level and the higher energy conduction band. Energy must be
applied for electrons to become free. The size and existence of this bandgap allows
one to visualize the difference between conductors, semi-conductors and insulators.
Bandgap can be either direct or indirect.
In direct bandgap materials, when an electron acquires enough energy, It can make a
transition from the edge of the valence band to the edge in the conduction band, when
the maximum of the valence band is at the same wave vector, k, as the minimum of
the conduction band, direct bandgap semi-conductors have a stronger absorption of
light as a result of a larger absorption co-efficient, direct bandgap materials are
generally efficient emitters and absorbers of optical energy because it is easy for

7
electrons to move between the conduction and valence band without having to
acquire or give off k (wave vector). They are also the appropriate semiconductors for
fabrication of light emitting devices. Typical examples are CdS, GaAs and ZnS.
In indirect bandgap materials, an electron cannot go from one band to another simply
by absorbing a photon of energy close to the bandgap, because the photon cannot
supply adequate wave vector.
The electron needs to acquire both energy and wave vector to make the transition in
indirect materials. At the band edges, there is the need for a three particle collision.
This three particle collision involves an electron, a photon and a phono, Phonons
have adequate wave vectors (K) but have little energy, while the opposite is true for
photons. If a photon and a phonon collide with an electron at the same time, the
electron acquires both enough energy and enough K to overcome the forbidden gap.
Such a three-body collision is almost unlikely. Examples of such materials are Si, Ge
and Gap (Berce et al., 2015)
2.5 Photoconductive Effect
Photoconductive effect is the increase in the conductivity of a material caused by
absorption of higher or lower radiation, this effect is most important in
semiconductor where the charge in conductivity is pronounced. When a photon of
sufficient energy is absorbed by semiconductor atom, an electron hole pair is
generated. The charge in conductivity is proportional to the number of electron hole
pair that are generated, provided that the charge in the carrier concentration is a small
function of the original carrier concentration.
2.6 Optical properties of materials
Optical property of a material is defined as its interaction with electromagnetic
radiation in the visible electromagnetic spectrum of radiation, which spans the wide
range from gamma rays with wavelength as 10-12, to radio waves with wavelengths
as long as 105 m. Visible light is one form of electromagnetic radiation with

8
 wavelength ranging from 380 to 700 nm. Light can be considered as having waves
and consisting of particles called photons.
Energy of a photon is given as,
hc
E= hv = λ (1)

h = Planck’s constant (6.62X10-34J.Sec)

V = Frequency
C = Speed of light in vacuum (3X108 m/sec),
λ = Wavelength.

When a material is illuminated with light, there are several processes that can occur
as a result of its interaction with the light. Some light may be lost and the energy
transform as heat in which case it is absorbed. Some, however, may pass through
without loss, that is, transmitted or scattered back from the surface of the material,
(reflection) as illustrated in figure 1

Fi g 1: Effect of incident light ray on

a material.

Different optical materials exhibit each of these phenomena. Absorption is the basic
mechanism needed for the detection of light, reflection is required for mirrors and
transmission is essential for optical components such as lens and prism. It is therefore
of fundamental importance to understand how these phenomenal arise. The basic
interaction which gives rise to all optical properties is that between the electromagnetic

9
(E.M) field of the light (particularly the electric vector) and the charge contain in the
material. This is always the basic process but its precise form depends very much upon
the nature of the charge and their distribution. That is, whether they are electronic or
ionic, whether they are free as in a metal or bound as in semiconductor or insulator
(Garbuny, 1965).

Semiconductor materials possess charges of all kinds, bound and free and so exhibit
some of the optical properties characteristics of each. The most important charges are
those associated with valence band and their excitation by inter band transition to the
conduction band. The net result of the inter band transition is to give rise to free
electrons and holes, which may or may not recombine at a later time (Butterworth,
1957). Non –metallic materials consist of various energy band structures. Thus,
absorption, reflection, transmission and refraction are all important for these materials.

2.6.1 Refraction

When light photons are transmitted through a material, they cause polarization of the
electrons and in turn the speed of light is reduced and the beam of light changes
direction. The relative velocity of light changes direction. The relative velocity of light
passing through a medium is expressed by the optical property called the index of
refraction (n), and is defined by:

Cv
n= (2)
C

where Cv is speed of light in a vacuum, C is the speed of light in the concerned

material. If the angle of incidence at normal to the surface is θ i, and the angle of
refraction is θr, the refractive index of the medium, n is given by figure2 (provided that
the incident light is coming from a phase of low refractive index such as vacuum or
air).

10
Fig 2: refraction of light ray

Speed of light in a material can be related to its electrical and magnetic properties as,

1
C = √ με (3)

1
And also, Cv = √ μ (4)
° ε°

When ε is permittivity, and μ is magnetic permeability. Thus, putting (3) and (4) into
(2) we have,

∁v √ με
n= = √ μ =√ μ r ε (5)
C °ε °
r

Since most materials are only slightly magnetic i.e μr =1 , Thus

n =√ με (6)

11
Table 1: Materials and their various refractive index.

Materials Refractive Index

Air 1.00

Water 1.33

NaCl 1.54

Silicon 3.29

ICE 1.31

Epoxy 1.58

Teflon 1.35

2.6.2 Reflection

Reflectivity is defined as fraction of light reflected at an interface, the illustration of n

material with light gives rise to the polarization of charges near to the surface and if
the energy of the polarization is not dissipated by interaction with lattice atoms, the
light is re-radiated, as from another oscillatory dipole. However, the re- radiated light
from the polarized charge could be emitted into the direction from which the incident
light had come from. If the surface contains a high density of easily polarized charges
which readily interact with the incident light, a very large proportion of the beam will
be reflected. This arises since even the re-radiation which is directed further into the
material will interact again with a high probability of being re-radiated back toward the
surface. The processes are not simple but the overall effect will be the reflection of
photon of the incident light (Lovell et al 1975)

Ii
R =I (7)
r
12
Where Ii and Ir are the incident and reflected beam intensities respectively, if the
material is in a vacuum or air then

( )
R = n+ n
n−n1
2
2
(8)

If the material is in some other medium with an index of refraction of n,

then; ( )
n−n1
R = n+ n
2
2

The above equations apply to the reflection from a single surface and assume normal
incidence. The value of R depends upon the angle of incidence. Materials with a high
index of refraction have a higher reflectivity than materials with a low index.

In metals, the reflectivity is typically on the order of 0.90 – 0.95, whereas for glasses it
is close to 0.05. The high reflectivity of metals is one reason that they are opaque.
High reflectivity is desired in many applications including mirrors, coating on glasses,
etc.

2.6.3 Absorption

When a light beam is impinged on a material surface, portion of the incident beam that
is not reflected by the material is either absorbed or transmitted through the material.
And according to Bouguer’s law: The fraction of beam that is absorbed is related to the
thickness of the materials and the manner in which the photons interact with the
structure.

I = I0 exp(- αx) (9)

Where I is the intensity of the beam coming out of the material, I i is the intensity of the
incident beam, X is the path through which the photons move and ⍺ is the linear
absorption coefficient, which is the characteristic of a particular material.
13
2.6.3.1 Absorption mechanism

Absorption occurs by two mechanisms: Rayleigh scattering and Compton scattering.

i. Rayleigh scattering: Where photons interact with the electrons orbiting an

atom and are deflected without any change in photon energy. This is significant
for high atomic number atoms and low photon energies. Example, Blue color in
sunlight gets scattered more than other colors in the visible spectrum and thus
making sky look blue. Tyndall effect is where scattering occurs from particles
much larger than the wavelength of light. Example clouds look white.
ii. Compton scattering: interacting photon knocks out an electron losing some of
its energy during the process. This is also significant for high atomic number
and low photon energies. Photoelectric effect occurs when photon energy is
consumed to release an electron from an atom. This effect arises from the fact
that the potential energy barrier for electron is finite at the surface of the metal.

2.6.4 Transmission

Fraction of light beam that is not reflected or absorbed is transmitted through the
material.

2.7 Beer Lambert law

The most frequent chemical applications of the Beer –Lambert law are analytic,
relying on the absorption of light in a solution (usually liquid, but sometimes solid or
gaseous) to provide a measure of the uniform concentration of light – absorbing solute.
When a sample of such as solution is confined within a cell with a path length x,
having walls that are parallel, planar and non-absorbing at the wavelength of interest,
the traditional form of the Beer –Lambert law asserts that

A= { }
I (0)
ln I ( x) = ECX (10)

14
Where I(0) is the intensity of monochromatic light entering the solution
perpendicularly to one face and I(X) is the intensity of light exiting the solution
through the opposite face. With an S.I unit of m 2mol-1, the constant E goes by a variety
of names, one which is molar absorptivity. The dimensionless quantity A, termed the
absorbance, is defined as the logarithm (sometimes decadic logarithms are used) of the
ratio of the incident light intensity to the transmitted light intensity. it is automatically
measured in modern photometric instrumentation. The transmittance T, is also
provided by many instruments; the expression

{ }
I (0)
T = I ( x) = exp {-ECX} (11)

gives its definition and its interpretation according to the Beer – Lambert law,

dI
dx
= ECI (12)

In which X is the dimension along which the light travels. This is a more fundamental
formulation, not being anchored to any particular geometry or experiment denoting the
cross sectional area of the cell, yet another way of stating the Beer- Lambert law is in
photochemical studies. In photochemistry the absorption of light leads to destruction or
transformation of the species that absorbs the light, this equation maybe shown to be
valid whether or not the concentration is uniform. This is as expected because it is the
number of light absorbing molecules present that is important, rather than their
distribution. In analytical applications of photometry, it is unusual to consider the
effect of non- uniform absorber concentration, because such a circumstance rarely
arises. The situation is different, however, if the absorber is photoconductive and
undergoes decomposition. In such a circumstance the concentration will generally
become non- uniform, even though the solution was homogeneous at the onset of the
experiment.

15
 2.8 Zinc Sulfide
Zinc sulfide occurs as two polymorphs, cubic spherelite and hexagonal wurtzite.
Spharelite is the stable phase at low temperatures and is a fairly common trace
mineral in sulfidic sediments. It forms as a discrete solid phase since Zn is not
incorporated to any significant extent within sedimentary pyrite (Luther et al., 1980;
Morse, 1994).
Zinc sulfide is an inorganic compound with the chemical formula ZnS. Zinc sulfide is
transparent and white in color, and both spharelite and wurtizite are intrinsic, wide
band gap semi-conductors it is usually produced from waste materials, and it is also a
by- product of ammonia synthesis using methane (Azjomo, 2013).

2.9 Review of Related Work on ZnS

Many researchers have worked on the optical properties of zinc sulfide thin film doped with
coper for instance Jayanthi et al., (2007) deposited ZnS:Cu nanoparticle thin film on a glass
slide with different copper concentrations using CBD. It was found; that the overall
photoluminescence intensity reached maximum at 0.01M% and quenched with further
increase in copper concentration. Enhancement of blue and green light emission by seven
and twenty-five fold respectively compared to undoped ZnS was observed in ZnS:Cu with
optimal dopant concentration. Optical absorption measurements indicate enhancement of
bandgap (3.89 eV) for undoped ZnS suggesting the quantum confinement effect in the
developed nanoparticle of size below the Bohr diameter.

Optical properties of ZnS:Cu can be thought of as any property that involves the interaction
between electromagnetic radiation or light and copper doped ZnS semiconductor including
absorption, diffraction, polarization, reflection and scattering effect (Mohammed, 2012;
Wang et al., 1987, Gao et al., 2001 and Nanda et al., 2002). Joshie et al., (2004) studied the
structure and optical properties of ZnS:Cu nanoparticles and the material found to have a
very important application in the manufacture of photo conductive infrared detectors,
transistors and contact rectifiers.
16
They also have very important application in areas of prisms, lenses and other components
of optical system. In view of this many researchers have worked on ZnS:Cu thin films for
instance Haranath and Chander, ( 2007) also deposited ZnS:Cu on glass slide using CBD at
353 k.

The result obtained by Nadeem and Ahmed, (2000) and Ndukwe (1996) on the optical
absorbance of ZnS thin films for wavelength in the infrared (up to 1000 nm) and visible
spectra showed that ZnS is practically non-absorbing in these regions. ZnS films deposited
on the glass substrates at room temperature have shown an enhanced absorption in the
neighborhood of λ = 330 nm (Huldt and Staflin, 1959, Gonellian, 1996) and 360 nm
(Nadeem and Ahmed, 2000) and were expected to have a fine grained structure. The
absorption peak shifts towards longer wavelength with increasing thickness. Ndukwe
(1996) also observed that some ZnS films have high absorbance (~0.56) in the near infrared
and low absorbance (~0.01-0.1) in the ultraviolet and visible region. Rood (1951) reported
that rapidly evaporated ZnS Film had a high optical absorption and claimed that the
deposition rate for producing good quality film should be about 0.16 nms -1, Polster (1952)
found that the rapidly deposited ZnS films (1.6 nms-1) had considerable light absorption, but
the films formed at about 0.5 nms-1 had negligible absorption. He claimed that large ZnS
crystals are formed at high deposition rates and this increased the amount of light lost by
scattering within the film. The result was opposite to the general experience because the
grain size of most substances falls as the rate of deposition increases. Decomposition of
evaporant may explain the greater light absorption of rapidly deposited ZnS thin films. At
high rates of evaporation corresponding to high source temperature, free zinc atoms may be
trapped in the condensed film. At low evaporation rates decomposition may be less and
there is also ample opportunity for free zinc atoms to oxidize either at the condensing
surface or in the region of the source. Zinc oxide has a refractive index comparable to that
of ZnS and if present the deposit would not be easily detected.

17
2.10 Thin Film

Thin film is a layer of material ranging from fractions of a nanometer to several

micrometers. The act of applying or depositing a thin film onto a surface or substrate is
termed thin film deposition. Thin is a relative term, but most of the deposition technique
control the layer thickness within a few tens of nanometers (Zainal et al., 1996). The
usefulness of the optical properties of thin films and the scientific curiosity about the
behavior of two dimensional solids has been responsible for the immense interest in the
study of science and technology of thin films. The technology and understanding of films
less than one (1) micron thick have made tremendous advances in the last 50 to 60 years
basically because of industrial demand for reliable thin film microelectronic devices
(Nadeem et al., 2005).

2.11 Types of Thin Film Deposition Techniques

In the past few decades, several deposition techniques such as chemical bath deposition,
close speed sublimation, thermal evaporation, spray pyrolysis, sputter deposition etc. have
been used in the deposition of thin film. Literature shows that Bunsen and Grove firstly
obtained metal films in 1852 by means of chemical deposition and flow discharge of
sputtering. Faraday made metal films in 1857 by the thermal evaporation on explosion of a
current carrying metal wire (Nadeem et al., 2005). In addition to a variety of new and future
based technology, thin film studies have directly and indirectly progressed in many new
areas of research in solid state physics and chemistry which are based on phenomena
uniquely characteristic of thickness, geometry and structure of films. Depending on the type
of material, various deposition methods can be employed.

2.11.1 Chemical Vapor Deposition (CVD)

This 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

18
decompose on the substrate surface to produce the desired deposit. Frequently, volatile by-
products are also produced, which are removed by a gas flow through the reaction chamber.

2.11.2 Successive Ion Layer Absorption And Reaction (SILAR) Method

The SILAR method is used to create coatings on thin films for technological products such
as photovoltaic cells that convert sunlight into energy for use in solar power application. By
allowing thin films to be coated in different chemicals at or close to room temperature,
metallic films or film incorporating metallic parts can use the SILAR method and avoid
possible problems with damage caused by oxidation or corrosion. SILAR requires the film
to be immersed in the chemicals required for creating a chemical solution over the substrate.
Between each immersion of the film into chemicals, the film is rinsed using purified water
to create the desired coating over the film.

2.11.3 Chemical Bath Deposition (CBD)

CBD is becoming an important deposition technique for thin films of compound materials
like chalcogenides (Hodes, 2002). A major success can be found in the recent period with
the deposition of semiconducting cadmium sulfide or ZnS or window layers in efficient
copper indium dislenids or cadmium or sulfide, or cadmium telluride thin film solar cells.
CBD takes advantage of the use of a reaction from solution where different precursors can
be dissolved easily either in the ionic or molecular form and react chemically on the
substrates leading to film formation. The key advantages are low cost, large area and low
temperature atmospheric processing (Lincot et al.,1999). This technique is a relatively
inexpensive, simple thin film process that is able to produce uniformly large area
deposition.

19
2.11.4 Electrophoretic Deposition

This is a rapid two-step process whereby the first step involves the particles acquiring an
electric charge in the liquid in which they are suspended. The particles are forced to move
towards one of the electrodes by applying an electric field to the suspension. In the second
step, the particles collect at one of the electrodes and form a consistent deposit on it; the
deposit takes the shape imposed by the electrodes.

2.11.5 Sputtering

This is a Physical Vapor Deposition (PVD) method of depositing thin films, this involves
ejecting a material from a target that is a source onto a substrate such as a silicon wafer,
Sputtered ions are ballistics which fly from the target in straight lines and impact
energetically on the substrates or vacuum chamber. Alternatively, at higher pressures, the
ions collide with the gas atoms that act as a moderator and move diffusively, reading the
substrates or vacuum chamber wall and condensing after undergoing a random walk. The
sputtering gas is often an inert gas such as argon which is not always readily available.

Thin films prepared by chemical methods are generally less expensive than those prepared
by other physical techniques. The chemical bath deposition method due to its many
advantages like low cost, large area production and simplicity in instrumental operation is
employed in this particular experiment. It may allow us to easily control the growth factor
such as film thickness, deposition rate and quality of crystallites by varying the solution PH,
temperature and bath concentration (Sankapal et al., 2004).

20
 CHAPTER THREE

3.0 MATERIALS AND METHOD

3.1 Materials

The following materials were used in the deposition of ZnS and ZnS:Cu thin film.
i. Zinc acetate
ii. Thiourea (CH4NaS)
iii. Copper acetate (C4H6CuO4)
iv. Distilled water
v. Triethanolamine (C6H15NO3)
vi. Trisodium citrate (Na3C6H5O7.2H2O) TSC
vii. Ammonia (NH3) 30%
viii. Glass substrate (frosted glass slide)
ix. Magnetic stirrer/heater
x. Beaker (100 mL and 150 mL)
xi. Weighing balance
xii. Oven
xiii. Furnace

3.1 Method
3.1.1 Substrate Preparation
Substrate cleaning is a very paramount /important process in thin film preparation. The
purpose of substrate cleaning is to enhance proper film deposition or adhesion onto the
substrate and to allow smooth and uniform deposition. There are also cleaned to remove all
unwanted particulate matter on it before deposition. The glass slides were thoroughly
washed by soaking them over night in nitric acid and washed in distilled water, placed in
ethanol for 30 mins and washed with distilled water, then allowed to dry in an oven before
usage. The ethanol was basically to de-grease the slides.
21
3.1.2 Experiment
In the synthesis of ZnS:Cu thin films using CBD technique, ZnS is doped with different
concentrations of copper, ranging from 0 M to 0.05 M at a constant concentration of ZnS .
In the first step, 25 mL of 0.33 M of zinc acetate, 8 mL of 0.25 M of sodium tricitrate and 5
mL of triethanolamine were mixed and stirred at 4000 rpm for 10 minutes to obtain a
homogenous complex solution. In the solution, 25 mL of 0.68 M of thiourea was mixed and
the mixture was stirred for another 5 minutes. Then 30% ammonia solution was added
dropwise in the solution to give a pH of 10.5.

Then well cleaned substrates were introduced into the solution. The temperature of
deposition was 353 k using a constant temperature water bath under continuous stirring.
The deposition was carried out for 2 hours and after which the coated films were removed
and rinsed with deionized water. Cleaning was necessary to remove absorbed impurities and
maximized particle agglomeration. The washed films were dried in the oven for about 30
minutes before annealing.
The same process was repeated for the doped films but this time with addition of 25 mL
each of 0.01, 0.02, 0.03, 0.04 and 0.05 molar percentage of copper acetate respectively for
the purpose of doping.
All the films were annealed at a temperature of 573 k for 1 hour, in order to;
a. Improve the crystallinity of the sample
b. Obtain desirable crystal phase
c. Eliminate residual stress
d. Remove water molecule
e. Remove contaminants.

22
3.2 Characterization Techniques

3.2.1 Absorption Measurement

The absorption spectra of all the deposited thin films were carried out using a JENWAY
UV- VIS spectrophotometer.
An uncoated glass slide was used as the reference slide. The wavelength was varied in units
of 10 from 200 - 1100 nm, and the corresponding absorbance readings were recorded.

3.2.2 profilometry: profilometry was carried out using a profiler, to determine the thickness
of the films. The thickness of the film is the major parameter in the hall measurement
machine since it helps in carrying out efficacious Hall Effect measurement.

3.2.3 Hall effect measurement.

Hall effect measurement machine was used to characterize three samples from the deposited
films in order to determine the mobility of the electrons and the Hall voltage so as to know
if the semiconductor is either P-type or N-tpe.

3.3.1 Hall Voltage of ZnS:Cu at different concentration of copper.

i. For ZnS:Cu at 0 M, the bulk concentration is 1.768 × 1012 cm-3 and charge of
Electron is 1.602 × 10-19 C.
1
Using, Hall voltage (VH) ¿ Bulk concentration ×charge of electron (13)
1
We have, VH ¿
1.768× 10 cm ×1.602 ×10−19 c
12 −3

1
=
2.8288× 10−7 c /cm 3
Therefore, VH = 3.5 × 106 cm3/c, which means ZnS is a p-type semiconductor.
ii. VH at 0.01 M
1
Using, VH ¿ Bulk Concentration ×Charge of eletron

23
 1
¿ 14 −3 −19
3.353× 10 cm × 1.602×10 C
5
10
¿
3.353× 1.602C / cm3
5
10
¿ 3
5.372C /cm
¿ 0.186 ×10 5 cm 3 /C

Therefore, VH at 0.01 M of ZnS:Cu is 1.86 ×10 4 cm3 /C , which means ZnS:Cu at 0.01
M is a P-type semiconductor.

VH at 0.05 M
1
¿
Bulk Concentration ×Charge of eletron
1
¿
7.719× 10 cm ×1.602 ×10−19 C
13 −3

6
10
¿ 3
7.719× 1.602C / cm

106
¿
12.366C /cm 3
6 3
¿ 0.081 ×10 cm /C

Therefore, VH at 0.05 M is 8.1 ×10 4 cm3 /C , which means ZnS:Cu at 0.05 M is a P-type
semiconductor.

24
 CHAPTER FOUR

4.0 RESULT AND DISCUSSION

4.1 Optical Absorption

The optical absorption spectra of the deposited ZnS and ZnS:Cu thin films were obtained
and analysed at room temperature over the wavelength range of 250 nm to 800 nm. Figure 3
to 8 shows the absorption spectral of the deposited films.

3.0

2.5
Absorbance (arb.units)

2.0

1.5

1.0

0.5

0.0
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Figure 3: Absorbance spectra of ZnS:Cu at 0 M

25
 0.6

0.5

Absorbance (arb.units)
0.4

0.3

0.2

0.1

0.0
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 4: Absorbance spectra of ZnS:Cu at 0.01 M

26
 0.45

0.40

0.35

Absorbance (arb.units)
0.30

0.25

0.20

0.15

0.10

0.05

0.00
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 5: Absorbance spectra of ZnS:Cu at 0.02 M

27
 0.45

0.40

0.35

Absorbance (arb.units)
0.30

0.25

0.20

0.15

0.10

0.05

0.00
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 6: Absorbance spectra of ZnS:Cu at 0.03 M

28
 0.24

0.22

0.20

0.18

Absorbance (arb.units) 0.16

0.14

0.12

0.10

0.08

0.06

0.04

0.02

0.00
250 300 350 400 450 500 550 600 650 700 750 800
Absorbance (nm)

Fig 7: Absorbance spectra of ZnS:Cu at 0.04 M

29
 0.22

0.20

0.18

0.16

Absorbance (arb.units) 0.14

0.12

0.10

0.08

0.06

0.04

0.02

0.00
250 300 350 400 450 500 550 600 650 700 750 800
wavelength (nm)

Fig 8: Absorbance spectra of ZnS:Cu at 0.05 M

30
Table 2: Peak Absorbance (A), maximum wavelength (λ) and wavelength of
absorption edges (λx) of the various deposited films.

Concentration (M) A (arb. units) (λ) (nm) λ x (nm)

0 2.74 329 692

0.01 0.59 300 425

0.02 0.44 311 423

0.03 0.42 319 448

0.04 0.19 336 460

0.05 0.21 300 441

The absorption spectra of ZnS:Cu thin films measured from 250 to 800 nm wavelength are
shown in figure 3 to 8. It can be observed generally from the graphs that the thin films have
higher absorption in the UV region and the absorption increased increased with an increase
in copper concentration as shown by the maximum absorption peak values in table 2. This
is due to the fact that the energy that excites photons for absorption is inversely proportional
to the wavelength of the photons according to Einstein relation. This implies that the energy
is higher at lower wavelengths resulting to higher absorption. The absorption is also
generally decreased with an increase in wavelength (figure 3 to 8). From the 0 M dopant
concentration to the sample at 0.05 M there is a huge blue shift which is as a result of either
a decrease in particle size or high carrier concentration caused by doping, though there is
fluctuation in the absorption edges. This result is similar to the one reported by
(Hasanzadeh, 2015).

Table 2 gives the summary of absorbance and absorption wavelength of the various
deposited films.
31
4.2 Transmittance

Figure 9 to 14 shows the optical percentage transmittance of the deposited thin films
prepared at room temperature at various concentration of copper ranging from 0 to 0.05 M
respectively.

50

45

40

35

30
Transmittance (%)

25

20

15

10

-5
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 9: Transmittance spectra of ZnS at 0 M

32
 80

70

60

50

Transmittance %
40

30

20

10

0
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 10: Transmittance spectra of ZnS:Cu at 0.01 M

33
 85

80

75

70

Transmittance (%) 65

60

55

50

45

40

35

30
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 11: Transmittance spectra of ZnS:Cu at 0.02 M

34
 90

80

70

60

Transmittance (%) 50

40

30

20

10

0
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

Fig 12: Transmittance spectra of ZnS:Cu at 0.03 M

35
 80

78

76

74

Transmittance (%)
72

70

68

66

64

62

60
250 300 350 400 450 500 550 600 650 700 750 800

Wavelength (nm)

Fig 13: Transmittance spectra of ZnS:Cu at 0.04M

36
 95

90

85

Transmittance (%) 80

75

70

65

60
250 300 350 400 450 500 550 600 650 700 750 800

Wavelength (nm)

Fig 14: transmittance spectra of ZnS:Cu at 0.05 M

37
Table 3: percentage transmittance and wavelength of the various deposited films.

Concentratio Transmittance Wavelength(nm)

n of copper (%)
(M)

0 0.32 323

0.01 26 300

0.02 36 309

0.03 38 318

0.04 64 327

0.05 62 299

The optical transmission spectra of ZnS:Cu films deposited at 80 ºC for different copper
concentrations are shown from figure 8 to 13. These spectra reveal that the transmittance is
high in the visible/near infrared region from 300-1000 nm. The high transmittance of the
films is a direct consequence of the wide bandgap. The transmittance is found to decrease
with the increase of copper concentration in ZnS. The decrease in transmittance at higher
doping concentration may be caused from the increased scattering of photons by crystal
defects created due to doping.

The above result in table 3 show clearly that the transmitted ray decreases as the
concentration of copper increases. The decrease in transmittance at higher doping
concentration may be caused from the increased scattering of photons by crystal defects
created due to doping. Similar result was reported by Rahman et al., (2011). Table 3 gives
the summary of percentage transmittance and wavelength of the various deposited films.
38
4.3 Determination of Optical Bandgap.

The optical bandgap of ZnS:Cu was determine from the plot of absorbance 2 against energy.
The absorbance2 versus energy graphs for ZnS:Cu films are plotted in figures 15 to 20.

39
 8

6
2
Absorbance (arb.unit)

4
2

0
1 2 3 4
Energy (eV)

Fig15: plot of absorbance2 against energy at 0 M

40
 0.35

2 0.30
(Absorbance) (arb.unit)
0.25

0.20
2

0.15

0.10

0.05

0.00
2 3 4
Energy (eV)

Fig 16: plot of absorbance2 against energy at 0.01 M

41
 0.20

2
Absorbance (arb. units)
0.15

0.10
2

0.05

0.00
2 3 4
Energy (eV)

Fig 17: plot of absorbance2 against energy at 0.02 M

42
 0.18

0.16

0.14
2
Absorbance (arb. units)

0.12

0.10

0.08
2

0.06

0.04

0.02

0.00
2 3 4
Energy (eV)

Fig 18: plot of absorbance2 against energy at 0.03 M.

43
 0.06

0.05
2
Absorbance (arb. units)

0.04

0.03
2

0.02

0.01

0.00

1 2 3 4
Energy (eV)

Fig 19: plot of absorbance2 against energy at 0.04 M

44
 0.05

0.04
2
Absorbance (arb.units)

0.03
2

0.02

0.01

0.00
2 3 4
Energy (eV)

Fig 20: plot of absorbance2 against energy at 0.05 M

45
The graphs of the square of absorbance are plotted against photon energy as seen in figure
15 to 20. By extrapolating the linear portion of the curves to the point of intercept on the
energy (hv) axis where A2 = 0, gives the bandgap. The estimated bandgap are shown in table
4. From figure 15 to 17, the trend shows that bandgap increased with an increase in copper
concentration however; there is a slight decrease again after the 0.03 M. this inhomogeneity
can be attributed to variation in crystallite sizes. The bandgap of the films varied between
2.04 to 3.13 eV, which shows that the increase in copper concentrations greatly affects the
bandgap of the semiconductor (ZnS).

The above bandgap range shows a lower bandgap than the one reported in literature by
Jayanthi et al., (2007) with bandgap of 3.89 eV for undoped ZnS, this may be because this
experiment was carried out at room temperature. Table 4 gives the summary of variation in
energy bandgap with concentration.

46
Table 4; Estimated bandgap of the ZnS:Cu at different concentrations.

Concentration Bandgap
of copper (M) (eV)

0 2.04

0.01 3.13

0.02 3.13

0.03 3.07

0.04 2.91

0.05 3.07

47
4.4 Profiler: profile of the film was carried out in order to determine the

thickness of the film, which was gotten to be 0.01 𝜇m. The picture of the

profile is as shown in figure 21.

Fig 21: The profile of ZnS.

4.5 Hall effect measurement.

48
Hall effect measurement machine was used to characterize three samples from

the deposited films in order to determine the mobility of the electrons, bulk

concentration, sheet resistance, resistivity, sheet concentration, conductivity

and the hall voltages at different concentration of copper, so as to know if the

semiconductor is either P-type or N-type. The result is as shown in table 4.

Table 4: Result of Hall Effect measurement

Concentration Hall Bulk Mobility Resistivity Conductivity

(M) Voltage concentration cm2/vs ῼcm 1/ῼcm
(v) (cm-3)

0 3.5×106 1.76×1012 1.145×102 3.380×104 3.342×10-5

0.01 1.68×104 3.353×1014 5.677×100 3.322×103 3.301×10-4

0.05 8.1×104 7.917×1013 1.544×101 5.795×108 1.787×10-4

The Hall Effect Measurement result shown in table 4 above indicates that the
semiconductor is P-type, since the values of the hall voltages at all concentration of copper
is positive.

CHAPTER FIVE
49
5.0 CONCLUSION AND RECOMMENDATION

5.1 Conclusion

Thin film of ZnS:Cu was successfully deposited using the chemical bath deposition
technique, the investigation of the optical properties was successfully carried out at room
temperature using UV- visible spectrophotometer.

The result of the optical measurement shows that the thin film absorbs more photon as the
concentration of copper increases

The transmittance of the film decreases with increase in copper concentration, this is
because of increased photon scattering by crystal defects created due to doping.

The bandgap varied significantly with change in copper concentration. t the thin film of ZnS
and ZnS:Cu has its bandgap in the range of 2.04 eV to 3.13 eV.

The thickness of the films was determined to be 0.01 𝜇m using a profiler.

Hall effect measurement shows that ZnS:Cu is a P-type semiconductor.

5.2 Recommendation.

In order to explore more optical and electrical properties of ZnS:Cu thin film analysis with
characterization and morphology:

i. I recommend that more research should be carried out on ZnS thin films using
Tauc’s relation, but with varying deposition time.
ii. I recommend that further researches be done on the structural and electrical
properties of ZnS:Cu nanoparticle thin film.
iii. I recommend that further researches be done to improve the crystallinity of thin
films.

REFERENCES

Al Kuhaimi, S.A. and Tulbah. Z., (2000). J. Electrochem, soc., 147, 214
50
Anur K., Ho S.M., Abdul Halim A., Norraini K., saravanam N., (2010). “Influence of the
deposition time on the structure and morphology of ZnS thin film deposited on indium
thin oxide thin films substrate” Arabian journal of chemistry 3(4), 234-249.
Beal, S.E., (1978). Cleaning and surface preparation, thin solid films, 53, 97.
Chopra K. L., Kainthla R. C., Pandra D.K and Takoor A. P., (1982). Physics of Thin Films,
12, 167.
Gilbert B., Frazer B. H., Zhang H., Huang F., Banfield J. F., Haskel D., Lang J. C., Srajer
G., De Stasio G. (2002). Quoted by Nasra B. T., Kamouna N., Kanzari M., 65
Greenwood N. and Earnshaw A., (1984). Chemistry of the elements, Oxford:
Pergamon, p. 1405, ISBN 0-08-022057-6
Hasse, M.A., Qui, J., Depuydt, J.M., Cheng, H., (1991). Appl. Phys. Lett., 59, 1272.
Hile D. D., Swart H.C., Motloung S.V., Pawade V. B., Kroon R.E., Egbo K. O., Koao L.F.
(2020) “Material Science in Semiconductor Processing”. Science Direct
https://doi.org/10.1016/j.mssp.2020.105118
Hile D. D., Swart H.C., Motaung S.V., Motaung T.E., Egbo K. O., Koao L.F. (2019)
“Superlattices and Microstructures”. Science Direct
https://doi.org/10.1016/j.spmi.2019.106222
Ilenikhena P. A., (2008). Comparative studies of improved Chemical Bath Deposited
Copper sulphide and Zinc Sulphide thin films at 320k and possible applications.
Journal of African Physical Review, 2: 0007 59.
Jayanthi K; Chawla S; Chander H; Haranath D (2007). National physical Laboratory, New
Delhi – 110 012, India.
Johnston D. A., Carletto M. H., Reddy K. T. R, Forbes I. and Miles R., (2002). W. Thin
Solid Films. 403-404 102-6
Kashani H., (1996). Thin Solid Films, 288(1-2).
Katsumi K., (1995). Jpn. J.Appl. Physics, pp 33, 4383.
Li, S.S., (2006). Semiconductor physical Electronics, Second Edition, pp. 246-253, p.355.
Nadeem, M. Y., Ahmed, W. (2000), Turk. J. Phys., 24651
Nadeem M. Y., Ahmed W., Wasiq M. F., (2005). ZnS Thin Films – An Overview. J of
Research (science); Buhauddin Zakaniya University, Multan, Pakistan-Vol.16, pp 105.
Nair P.K., Nair M. T.S., Garcia V. M., Arenas O. L., Pena Y., Castillo A., YaLA T
Ndukwe, I.C (1996) Solar Energy Materials and Solar cells, 40, 123
51
O’Brien, P. and J. Mc Aleese, (1998), Quoted by Vaughn Edelson (2007). Concentration
Crisis in Brown Alumni Magazine, July/August 2007.
Ohring, M., (1992). The Material Science of Thin Films, Academic Press, San Diego. Pp.
195-199, 336-339. Padam G. K., Rao S.U.M. and Maholtra G. L. (1988), J. Appl.
Phys., 63, 770
Petterson, J.D. and Bailey, B. C., (2005). Solid-state Physics introduction to The theory, pp.
293-294, 113, 637.
Polster, H.D (1952), J. Opt. soc. Amer, 42, 43.
Rahman F., Podder J. and Ichimura, M. (2011) “Study on Structural and Optical
Characterization of In-Zn-S Ternary Thin Films Prepared by Spray pyrolysis”
International Journal of Optics and Photonics (IJOP) Vol. 5, No. 2
Savado O. (1998), Sol. Energy Mat. Sol. Cells 52, 361
Singh, J., (2003). Electronic and Optoelectronic properties of Semiconductor Structures,
Cambridge University Press; New York, P. IV, 51-52.
Singh, J., (2006). Optical properties of Condensed Matter and Applications, John Wiley and
Sons, Ltd. Pp. 2-4.
Tan W. C. (2006). Optical properties of amorphous selenium films thesis, University of
Saskatchewan, pp. 3-13.
Tauc, J., (1974). Amorphous and Liquid Semiconductors, Plenum: New York, P. 159.
Venables, J.A., (2003). Introduction to Surface and Thin Film Processes, Cambridge
University Press. Cambridge. Pp 5-60.
Vipin, K., Sharma, M.K., Gaur, J., Sharma, T.P., (2008). Polycrystalline ZnS Thin Films by
screen printing Method and its Characterization, J Chalcogenide Letters Vol.5, No 11:
pp 289, 291.
Wells, A. F. (1984), Structural Inorganic Chemistry (5 th ed.), Oxford: Clarendon Press,
ISBN 0-19- 855370-6
Yacobi, B. G., (2004). Semiconductor Materials: An Introduction to Basic Principles, pp. 1-
3, 154-157, 107.
Young, H.D. and Freedman, R.A., (2008). University physics with Modern Physics, 12 th
Edition, pp. 1449 – 1455.
Zainal Z., Zobir Hussein M., Ghazali A., (1996). Solar Energy Materials and Solar Cells,
40, 347.

52