See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/331843610

Synthesis of Cadmium Sulfide quantum dot and studying it's optical and
structure properties

Thesis · March 2009

DOI: 10.13140/RG.2.2.35750.16964

CITATIONS READS

4 1,297

1 author:

Omar Adnan
University of Baghdad
25 PUBLICATIONS 89 CITATIONS

SEE PROFILE

All content following this page was uploaded by Omar Adnan on 18 March 2019.

The user has requested enhancement of the downloaded file.

 Republic of Iraq
Ministry of Higher Education
and Scientific Researches
University of Baghdad

Synthesis of Cadmium Sulfide quantum

dot and studying it's optical and
structure properties

A Thesis
Submitted to the College of Science, University of Baghdad
In partial Fulfillment of the Requirements for the Degree of
Master of Science in Physics

by
Omar Adnan Ibrahim
(B. Sc. In Physics 2006)

Supervised by
Asst. Prof. Dr. Abdulla M.Suhail

Rabeialawl March
1430H 2009AC
To
My Mother
 Supervisor Certification

We certify that this thesis was prepared by Mr. Omar A. Ibrahim

under our supervision at the physics Department, College of Science,
University of Baghdad as partial requirement for the degree of Master
in Physics Science.

Signature
Name : Abdulla M.Suhail
Title : Asst. Prof.
Address : College of Science, University of Baghdad.
Date : / / 2008.

In view of the available recommendations, I forward this thesis

for debate by the examination committee.

Signature
Name : Bahaa T.Chiad
Title : Professor
Address : College of Science, University of Baghdad.
Date : / / 2008.
 Acknowledgments
First and foremost, I'd like to thank god for saving, protecting me and giving me
faith and strong to complete my research.

I wish to express my deepest appreciation to all the people that have contributed
to the completion of this thesis.

I would like to express my deep gratitude and appreciation to my supervisors

Dr. Abdulla M.Schail for suggesting the topic of the thesis, continuous advice
and their guidance through out this work.

I am grateful to the Dean of the college of science and the chairman of physics
department for their help.

I would like to thank Dr. Mohammed T. Hussein and Dr. Nathera A. ali for
guidance through out this work.
My thanks are extended to the staff of Laser and Molecular laboratory,
especially Mohammed Abdullah Hameed and Sarmed Salih Al-Awadi for
their help.

Finally, it will be unfair on my part if I don’t mention the support rendered by

my mother, lovely brothers and sisters.

Omar
Contents:

Chapter One: Introduction and Basic Concepts

1.1 Introduction.............................................................................1
1.2 The aim of the work................................................................2
1.3 Synthesis Methods of Quantum Dots.......................................3
1.3.1 Epitaxial Growth Techniques.........................................3
1.3.2 Electron beam lithography.............................................5
1.3.3 Colloidal Synthesis of Quantum Dots............................5
1.4 Literature survey.....................................................................7
1.5 Quantum Confinement in Semiconductors..............................10
1.6 Optical Properties of CdS......................................................11
1.7 Type of Confinement in Semiconductors................................13
1.7.1 one – dimension confinement (quantum well)................13
1.7.2 Two – dimension confinement (quantum wire)………...16
1.7.3 Three – dimension confinement (quantum dot ).............16
1.8 Density of states....................................................................17
1.9 The applications of the quantum dots…………...…………....22
1.9.1 Applications engineering …………………….…...........23
1.9.2 Applications Biology ….………………………...………24

Chapter Two: The Experimental Work

2.1 Introduction…………………………………………………...28
2.2 The chemical spray pyrolysis method for preparation
CdS quantum dot……………………………………………...29
2.2.1 The chemical spray pyrolysis system ………………….29
2.2.2 The preparation of spray solution………………………31
2.2.3 Substrate preparation for spray…………………………32
2.2.4 Synthesis of CdS film…………………………………..33
 2.2.5 Synthesis of CdS quantum dot………………………….34
2.3 Synthesis colloidal of CdS quantum dot……………………….35
2.3.1 System for colloidal CdS quantum dot preparation…….36
2.3.2 Synthesis colloidal CdS quantum dot by
using nanoparticles……………………………………...37
2.3.3 Second method for Synthesis colloidal
CdS quantum dot……………………………………….39
2.3.4 Synthesis of colloidal CdS quantum dot………………..40
2.4 Optical Properties……………………………………………..40
2.5 CdS quantum dot morphology study………………………….42
2.6 X – Ray diffraction study……………………………………...44

Chapter Three: Results and Discussions

3.1 Introduction………………………………………………………45
3.2 Characteristics for CdS film synthesis by chemical
spray pyrolysis……………………………………………………45
3.2.1 X-Ray diffraction results for CdS film.………………………....45
3.2.2 Optical properties of CdS film………………………………….46
3.3 Characteristics for CdS quantum dot synthesis by
chemical spray pyrolysis……………………………………….50
3.3.1 CdS quantum dot morphology study by optical microscope…..50
3.3.2 Optical properties of the quantum dot………………………….52
3.4 Characteristics for colloidal of CdS quantum dot………………59
3.4.1 X-Ray diffraction results for CdS.……………………………...59
3.4.2 The optical properties of CdS quantum dot……………………64
3.4.3 CdS quantum dot morphology study by
transmission electron microscope …..………………………...69
3.5 Conclusion……………………………………………………….71
3.6 Suggestions for Future Work…………………………………….71
References …………………………………………………...72
Abstract :

The aim of this research is to prepare CdS quantum dot and to study its
structural and spectroscopic properties.
Two methods were used for the preparation: the first is a chemical spray
pyrolysis and the second is the chemical method.

- Chemical spray pyrolysis

The first method for preparation of CdS quantum dot is based on chemical
spray pyrolysis. The sample were prepared by spray a mixture of CdCl2 solution
with CS(NH2)2 solution on glass slides containing nanometer defects (La2O3and
dust).
The energy band gap was calculated from the absorption spectrum and we
notices an increase in energy gap by (0.19 and 0.3) eV respectively which gives
the quantum dot size of CdS quantum dot to be about (6.3 and 5) nm. Also the
emission spectrum was measured to calculate the change in energy gap by (0.15
and 0.4) eV respectively. This means that the size of CdS quantum dot obtained
was (7 and 4.34) nm respectively.
The second method for preparation of CdS quantum dot was by chemical
spray pyrolysis using a mixture of CdCl2 solution with CS(NH2)2 solution and
La2O3 nanoparticles and the absorption spectrum was measured to calculate the
energy gap . Also we noticed an increase in energy gap by (0.18) eV and the
calculated quantum dot size of CdS quantum dot was (6.4) nm.
As well as the calculation of energy gap was done by emission spectrum which
gives a increase in energy gap by (0.19) eV and the calculated CdS quantum dot
size was (6.3) nm. All the tests by optical microscope, using visible and UV to
illuminate the sample and photographed by color digital camera, shows a yellow
color which represents the formation of CdS quantum dot and selectivity PL
calculated gives a blue dots which represent the quantum dot of the energy gap.
- The chemical method

The first method for preparation of CdS quantum dot was performed by
reaction of solutions of CdCl2 and CS(NH2)2 on nanoparticles as a base for the
reaction. The reaction was done in an alkaline medium.

Form the absorption spectrum, the calculated energy gap was creased in by
(0.26) eV and the quantum dot size of the prepared CdS quantum dot was (5.38)
nm. Also an increase of the energy gap was noticed, by using emission
spectrum, by (0.25) eV and the quantum dot size (4.49) nm.

By using X-ray spectrum the calculated quantum dot size was (7.3) nm

The image of the samples were viewed by transmission electron microscope

(TEM) and from the shape of the formed CdS quantum dot.

The second method for preparation of CdS quantum dot was by chemical
method using reaction of S with CdCl2 in oleylamine as a support for the
reaction. The energy band gap was calculated from the absorption spectrum and
we noticed an increase in energy gap by (0.18) eV which gives the quantum dot
size of CdS of (6.47) nm. Also the emission spectrum was measured to calculate
the increase in energy gap by (0.19) eV. This mean that the size of CdS quantum
dot is (6.29) nm.
By using X-ray spectrum the calculated quantum dot size was (5.27) nm.
The formation of CdS quantum dot was checked by TEM image.
 List of Symbols and Abbreviations:

Symbol Description
IR Infrared radiation
DNA Deoxyribonucleic acid
PL Photoluminescence
CdS Cadmium Sulfide
UV Ultraviolet radiation
MBE Molecular Beam Epitaxy
MOCVD Metal-organic chemical vapor deposition
LAVD Laser-assisted vapor deposition
EBL Electron beam lithography
NCs Nanocrystals
NPs Nanoparticles
TEM Transmission Electron Microscopy
HRTEM High Resolution Transmission Electron Microscopy
eV Electron Volt (unit of energy)
FTIR Fourier Transform Spectroscopy
VIS Visible radiation
c-CdS Crystalline Cadmium Sulfide
h Planck's constant
m* Effective mass
t thickness
A Absorbance
ε Material Permittivity (F/m)
d Confinement diameter (nm)
e Electron charge (col)
aB Bohr radius (Aº)
μ* Electron –hole reduced mass
me* Effective mass for electron
mh* hole mass for electron
q.w Quantum well
q.wire Quantum wire
q.dot Quantum dot
k Wave vector
LED Light Emitting diode
EC Coulomb interaction energy
me electron mass
mh Hole mass
Eg Energy gap (eV)
Egbulk Energy gap of bulk(eV)
Egq.dot Energy gap of quantum dot (eV)
ºC Centigrade degree (unit for measuring the temperature)
CdCl2 Cadmium Chloride
CS(NH2)2 Thiourea
S-2 Sulfur ion
Cd+2 Cadmium ion
w.t Weight
M.wt Molecular weight
M Molarity
La2O3 Lanthanum Oxide
α The absorption coefficient (cm-1)
hυ The photon energy (eV)
υ Frequency
 Wavelength
FWHM Full Width at Half Maximum
ASTM American Society for Testing and Materials
hkl Miller indices
RNA Ribonucleic acid
siRNA Small interfering RNA
 List of figures:

figure Title P
The x-rays being shined through a mask. The X-ray
1-1 light reacts with the photo-resist on the wafer to create 5
quantum dots
1-2 Zing – blend lattice for CdS 11
1-3 types of electron confinement 13
1-4 Illustration of type I and II quantum well 14
1-5 The density of states in different confinement 17

1-6 multicolor quantum dot probes injected into a mouse 26

can detect and track multiple tumor targets
2-1 Chemical spray pyrolysis system setup 28
2-2 Diagram of the atomizer 29
2-3 The controller circuit for chemical spray pyrolysis 30
2-4a defected the sample by dust 33
2-4b Defected the sample by La2O3 33
2-5 System for colloidal CdS quantum dot preparation 35
2-6 the absorption spectrophotometer 40
2-7 the fluorescence spectrophotometer 40
2-8 the optical microscope 42
2-9 the Transmission Electron microscope 42
The X-ray diffraction for CdS film of 0.1M
3-1 44
concentration
The X-ray diffraction for CdS film of 0.5M
3-2 45
concentration
The absorption spectrum for CdS film of 0.1M
3-3 46
concentration
The absorption spectrum for CdS film of 0.5M
3-4 46
concentration
(αhυ) 2 vs. photon energy for CdS film of 0.1M
3-5 47
concentration
(αhυ)2 vs. photon energy for CdS film of 0.5M
3-6 47
concentration
The fluorescence spectrum for CdS film of 0.1M
3-7 48
concentration
The fluorescence spectrum for CdS film of 0.5M
3-8 48
concentration
3-9a CdS q.dot on dust nanoparticles 49
3-9b CdS q.dot on La2O3 nanoparticles 49
3-9c CdS q.dot constructed by spray the colloidal mixture 50
3-10a CdS q.dot on dust nanoparticles 50
3-10b CdS q.dot on La2O3 nanoparticles 50
3-10c CdS q.dot constructed by spray the colloidal mixture 51
The absorption spectrum for CdS quantum dots
3-11a 51
On dust nanoparticles
The absorption spectrum for CdS quantum dots
3-11b 52
on La2O3 nanoparticles
The absorption spectrum for CdS quantum dots
3-11c 52
by sprayed colloidal mixture
(αhυ)2 vs. photon energy for CdS quantum dot on dust
3-12a 53
nanoparticle
(αhυ)2 vs. photon energy for CdS quantum dot on
3-12b 54
La2O3 nanoparticle
(αhυ)2 vs. photon energy for CdS quantum dot by
3-12c 54
spray the colloidal mixture
The fluorescence spectrum for CdS quantum dot on
3-13a 55
dust nanoparticles
The fluorescence spectrum for CdS quantum dot on
3-13b 56
La2O3 nanoparticles
The fluorescence spectrum for CdS quantum dot
3-13c 56
prepared by spray the colloidal mixture
The X-ray diffraction for the yield at room temp.
3-14a 58
The reaction time is 3 hours
The X-ray diffraction for the yield at room temp.
3-14b 59
The reaction time is 6 hours
The X-ray diffraction for the yield at 90°C.
3-15a The reaction time is 3 hours 60

3-15b The X-ray diffraction for yield by using oleylamine 61

The absorption spectrum for the CdS quantum dot
3-16a synthesized using nanoparticles at 90°C. The reaction 63
time is 3 hours
The absorption spectrum for CdS quantum dot
3-16b 63
synthesized by using oleylamine
(αhυ)2 vs. photon energy for the CdS quantum dot
3-17a synthesized by using nanoparticles at 90°C. The time 64
reaction is 3 hours
(αhυ)2 vs. photon for CdS quantum dot by using
3-17b 64
oleylamine
 The photoluminescence spectrum for the CdS
3-18a quantum dot synthesized by using nanoparticles 90°C. 65
the time reaction is 3 hours
The photoluminescence spectrum for CdS quantum dot
3-18b 66
by using oleylamine
3-19 photon excited emission spectra of CdS quantum dot 67
(TEM) images for the CdS quantum dot synthesized by
3-20a 68
using nanoparticles at 90°C. the reaction time is 3hours
(TEM) images for CdS quantum dot synthesized using
3-20b 68
oleylamine
(TEM) images for CdS quantum dot synthesized using
3-20c 69
oleylamine

1.1 Introduction

A quantum dot is a semiconductor nanostructure that confines the motion

of conduction band electrons, valence band holes, or excitons (bound pairs of
conduction band electrons and valence band holes) in all three spatial directions
[1][2][3]
.
The quantum dot have been extensively studied by scientists and engineers over
the past decades because of their unique size dependent optical properties (the
size of the dots is much larger than the exciton Bohr radius) [4], which are very
different from their bulk counterparts because of quantum mechanical effects [5].
A broad range of applications in many different disciplines for quantum
dots have been proposed. The applications include the use of the quantum dot as
[6]
optoelectronic devices , information storage. The semiconductors with
quantum dot dimensions are used as materials for cascade lasers[7], materials for
infrared radiation (IR)[8] , photo-detectors injection lasers, color coded quantum
dots for fast DNA testing and 3-D imaging inside living organism.
Because of their very small size, quantum dots exhibit different optoelectronic
behavior than bulk semiconductors of the same composition [4]. In particular, the
confined dimensions result in a quantization of the bulk electronic bands and a
widening of the gap (called a blue shift) between the valence band and
conduction band, which is size dependent [9]. Thus a quantum dot can be seen in
analogy to the “particle in a box” model (or “particle in a sphere” model) [10] .
The CdS quantum dot is a semiconductor, it's a compound containing an
element from periodic table groups ΙΙ (Cadmium) and groups VΙ (Sulphur), that
have been extensively used as a light emitting diode LED
(blue emitting devices ) [11] .
This material is used as photovoltaics, flat-panel displays, and in other optical
devices based on its nonlinear properties [12].

1.2 The aim of the work

In this work we are going to present some methods of the synthesis and
testing of the CdS quantum dot, can be classified as CdS material:
The synthesis methods are:
1-Spray of the aqueous mixture of cadmium chloride solution (CdCl2) and
thiourea solution (CS (NH2)2 by chemical spray pyrolysis on the slides of glass
defected by nanoparticles.
2- Spray of colloidal solution, that contains aqueous mixture of (CdCl2) and
(CS(NH2)2) and Lanthanum oxide (La2O3) nanoparticles , by chemical spray
pyrolysis on slides of glass .
3- Interaction of the aqueous (CdCl2) solution with aqueous (CS(NH2)2) solution
on the nanoparticles in alkaline midst.
4- Interaction of (CdCl2) with (S) in the oleylamine solution is the interaction
midst.
5-The prepared quantum dot was tested by:
X-ray diffraction,
Optical spectra (absorption and emission)
Optical microscope (visible and UV illumination)
Transmission electron microscope to determine the crystal size.
6- The emitted peak is used to study the energy gap and the size of the formed
quantum dots.
The relation between the energy gap and the quantum dot size was
demonstrated as well.

1.3 Synthesis Methods of Quantum Dots

Depending on their applications, high quality quantum dots of various

semiconductor materials have been synthesized either on a substrate or dispersed
in (organic/inorganic) solution. Some of the major methods used to fabricate
quantum dots are described in this section.
1.3.1 Epitaxial Growth Techniques

Molecular Beam Epitaxy (MBE) is a widely used technique for epitaxial

growth of quantum-confined structures of both II-VI and III-V compound
semiconductors as well as silicon and germanium. The growth is carried out in
an ultrahigh vacuum chamber, where the atoms that are the constituents of the
semiconductors to be grown are evaporated by heating the effusion cells or
ovens. The vapor passes through a small orifice, accelerated by the pressure
differential on two sides of the orifice, and, thus, forms a molecular beam.
Because of the low density of this molecular beam, the particles neither react nor
collide with each other before they impinge on the substrate mounted on the
opposite side of the chamber. By monitoring and controlling the fluxes from
different cells together with the substrate temperature, the composition and the
epitaxial growth rate on the substrate can be precisely controlled. The ultra high
vacuum chamber in MBE allows the use of many in situ analytical techniques to
characterize the condition of the substrate surface prior to growth and the
 [13]
crystallinity, composition, and thickness of the epitaxial material . The MBE
[14]
technique is well suited for fabrication of quantum wells , quantum wires [15]
and quantum dots [16]. The quantum well growth can be precisely controlled
layer by layer. The fabrication of quantum wires and quantum dots can be
realized by using substrates with a patterned surface.
Another form of quantum dot array, three-dimensional islands on a
substrate, can be synthesized when there is a large strain between a thin epitaxial
layer and the substrate due to a significant lattice mismatch between the two
materials. The surface reconstruction, facilitated by the substrate temperature,
results in the formation of three-dimensional structures, composed of the
epitaxial material at regular spacing across the surface of the substrate. MBE
technique has revolutionized the semiconductor technologies and widely used in
[16]
manufacturing quantum dot , which involve MBE-growth quantum well and
quantum dot structures.
Metal-organic chemical vapor deposition (MOCVD) is another commonly
used epitaxial growth method in which the semiconductor structure are grown
from the precursors of metal organics and hydrides. In a MOCVD process, the
suitable precursors of semiconductor in gas form are transported to the reaction
chamber, and then deposition and growth of the semiconductor take place on a
substrate. Finally, the remaining decomposition products are removed from the
chamber. Self-assembled GaN quantum dots were grown on the Al xGa1-xN

surfaces using a surfactant has been reported [17].

Generally, MOCVD offers the advantage of being a simple and faster growth
technique, with a growth rate typically 10 times than that of MBE. However, the
precursors are highly toxic and, thus, require extreme safeguard and care during
handling. In addition, the hydrodynamic condition of gas flow does not permit
the extensive in situ characterization.
Another technique to grow quantum dots on a substrate that have evolved
in recent years is laser-assisted vapor deposition (LAVD), in which the
deposition materials ablated by lasers are directly deposited onto the substrate or
mixed with a reactive gas to produce the appropriate material [1].

1.3.2 Electron beam lithography (EBL)

This process is a little like etching a chip. A mask is created with an
electron beam that has many tiny holes in it. Then evaporated chemicals,
similar to the ones used in epitaxy, are sprayed through the mask on to a
substrate, creating many little balls, as shown in figure (1-1). This process has
some of the same shortcomings as epitaxy, mainly that the quantum dots are still
connected to the substrate after synthesis. Additionally, scientists have found it
difficult to create such small masks that need to have holes just nanometers in
diameter. Lithography was originally a very popular process for creating
quantum dots; however, this process creates many defects and is slow compared
to the other processes [18].

Fig (1-1): The x-rays being shined through a mask. The X-ray light reacts
with the photo-resist on the wafer to create quantum dots.
1.3.3 Colloidal Synthesis of Quantum Dots

An alternative approach is to produce quantum dots in solutions, called

colloidal synthesis, which deals with chemical reactions in solution on a
nanometer scale. Colloidal synthesis has been conducted to make semiconductor
nanostructures of different composition, size and shapes. This method involves
growing nanoparticles of inorganic materials through chemical reaction of their
precursors and, sometimes, controlled precipitation of the reaction product in
certain solvents.
Generally, the growth process starts with the fast formation of a huge
number of nuclei. Then more and more of the solid product deposits onto the
nuclei, so the sizes of the crystallites grow slowly till the desired size is reached,
at which time the reaction must be quenched. Otherwise, the dots could keep
growing under a process, known as Ostwald ripening, which is the growth of
larger dots through the transfer of material from smaller ones, which have a
higher solubility [ 19].
The methods which used in colloidal synthesis of quantum dot Thermal
evaporation process, and tem plating technique [20].
1.4 Literature survey
Here we are going to present the previous work of the CdS quantum dot
preparation techniques and the results of the different preparation methods.

P. Nandakumar et al. in 2001 studied Quantum confinement effects on the

longitudinal optical and acoustic phonons in CdS nanocrystals (NCs) in the
strongly confined regime in the polymer matrix Nafion using Raman
spectroscopy. The LO-phonon modes show size-dependent asymmetric
broadening though the broadening and asymmetry are less than those predicted
by the phonon confinement models [21].
W. William Yu et al. in 2003 found the extinction coefficient per mole of
nanocrystals at the first exitonic absorption peak, for high-quality CdTe, CdSe,
and CdS nanocrystals to be strongly dependent on the size of the nanocrystals,
between a square and a cubic dependence. The measurements were carried out
using either nanocrystals purified with monitored purification procedures or
nanocrystals prepared through controlled etching methods [22].

Z. Yu, et al. in 2003 studied the electronic spectrum of CdS colloidal

quantum dots with a radius of 1.0-2.3 nm by low-temperature
photoluminescence excitation spectroscopies. CdS quantum dots are found to
exhibit a resonant Stokes shift of ~20-70 meV, which is ~4 times larger than
similarly sized CdSe QDs. This effect can be reproduced [23].

J. Joo et al. in the same year reported the synthesis of semiconductor

nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive
synthetic process. CdS nanocrystals that consist of rods, bipods, and tripods
were synthesized from a reaction mixture containing a 1:6 molar ratio of
cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained
from a reaction mixture with cadmium to sulfur molar ratio of 2:1. All of the
synthesized nanocrystals were highly crystalline [24].

Y. Li, et al. in 2005 prepared polystyrene microbeads doped with highly

luminescent CdS quantum dots. Polystyrene particles with diameters ranging
from 100 nm to 500 nm were prepared by a suspension polymerization method
and with different loadings of quantum dots. Confocal microscopy and
photoluminescence studies proved that the CdS nanoparticles were evenly
distributed throughout the polystyrene spheres. The quantum dot containing
composites have similar optical properties to isolated CdS quantum dots [25].

H. Zhang, et al. in 2006, demonstrated the preparation of ZnS

nanoparticles by spray pyrolysis using zinc diethyldithiocarbamate as a single-
source precursor. The nanoparticles (NPs) were characterized by transmission
electron microscopy (TEM), highresolution TEM (HRTEM), and optical
spectroscopies. The NPs are about 3 – 20 nm in diameter and are crystalline, as
indicated by the presence of lattice fringes in HRTEM, and by selective-area
electron diffraction. The UV absorption spectrum showed peaks in the range of
330-380 nm, and the nanoparticles exhibited bright blue photoluminescent
emission under UV illumination [26].

The same group in 2006 demonstrated the vapor-phase synthesis of TeO2

nanoparticles from a dilute solution of telluric acid, Te(OH)6, that is dispersed
into fine droplets by an atomizer.
These droplets are carried through a furnace, where they evaporate and
where the precursors react to nucleate TeO2 particles. The nanoparticles were
characterized by TEM, FTIR and X-ray diffraction. The effects of operating
parameters on nanoparticle composition, production rate and size were also
studied. This laboratory-scale process is capable of producing milligram to gram
quantities of amorphous TeO2 nanoparticles with primary particle diameters
from 10 to 40 nm [27].

K. Yong et al. in 2006 reported here straightforward solution-phase

methods of preparing CdS nanocrystals (NCs) with a wide variety of
morphologies, starting with oleylamine as the surfactant or capping agent, and
varying the reaction conditions. We have systematically investigated the effects
of temperature, precursor concentration, growth time, addition of metal
nanoparticles, addition of cosurfactants, and acidification of the reaction
medium on the growth of CdS NCs. These parameters have a tremendous
impact on the morphology of the nanocrystals, allowing the controlled synthesis
of a series of shapes including nanorods, bipods, tripods, tetrapods, nanocubes,
nanowires, chain-like nanostructures, and nanoplatelets. At 100 °C, in the
absence of secondary additives, they observed the nucleation of zinc blend CdS
cores, followed by the growth of wurtzite arms to produce rods, bipods, and
tripods. The addition of tetradecylphosphonic acid suppressed the growth of the
wurtzite arms, resulting in zinc blend cubic nanocrystals. The addition of gold
nanoparticles or acidification of the reaction medium led to nucleation and
anisotropic growth of the wurtzite polymorph [12].

Y. Wu et al. in 2007 studied the characterized several spectroscopic

properties of commercial, streptavidin functionalized quantum dots (QD525, lot
1005-0045, and QD585, lot 0905-0031, from Invitrogen). This is the first step in
the development of calibration beads to be used in a generalizable quantification
scheme of multiple fluorescent tags in flow cytometry or microscopy
applications. They used light absorption, photoexcitation, and emission spectra,
together with excited state lifetime measurements, to characterize their
spectroscopic behavior, concentrating on the 400- to 500-nm wavelength ranges
that are important in biological applications. Their data show an anomalous
dependence of emission spectrum, lifetimes, and quantum yield (QY) on
excitation wavelength that is particularly pronounced in the QD525. For QD525,
QY values ranged from 0.2 at 480 nm excitation up to 0.4 at 450 nm and down
again to 0.15 at 350 nm. For QD585, QY values were constant at 0.2 between
500 and 400 nm, but they dropped to 0.1 at 350 nm [28].

S. Nath, in 2008 reported the synthesis of CdS and ZnS quantum dots via
a chemical route. The samples have been analyzed by UV/VIS absorption
spectroscopy and High Resolution Transmission Electron Microscopy. These
characterization techniques indicate the formation of quantum dots with a
particle size less than 10 nm. These results indicate their potential application in
electronics as nano tuned devices and nano high pass filters [8].

1.5 Quantum Confinement in Semiconductors

The electron-hole pair in a quantum dot is tightly confined in all three

dimensions, known as quantum confinement, which produces a number of
pronounced modifications in the optical properties of the semiconductor [4].
To have a better understanding of quantum confinement, we will start with a
discussion of the properties of the bulk materials.

1.6 Optical Properties of CdS

The crystalline cadmium sulphite (c-CdS) has Zinc- blend lattice structure
[29]
as shown in figure (1-2) . It has relatively wide and direct band gap of
approximately (2.42 eV). The pure (c-CdS) has excitation binding energy in
order of (29 meV) [30] and Bohr radius of (2.8 nm) [12].
The radiative recombination of exited electrons in conduction band and holes in
the valence band is direct and the photoluminescence (PL) lifetime is in the
order of 10-4 sec [31].
CdS is a very useful optoelectronic, piezoelectronic and semiconducting
material. The thin films of CdS are of considerable interest for their efficient use
in the fabrication of solar cells [30].

Fig (1-2) Zinc – blend lattice for CdS[29]

Semiconductors are often classified by the periodic table groups to which they
belong.
Table (1-1) lists some bulk phase physical properties of several common
semiconductors, including their band gap energies, corresponding wavelengths,
exciton Bohr radii, and exciton binding energies.
Table (1-1) Material parameters for several common semiconductors[12][8][33]

Periodic Band gap Band gap Exciton Exciton

Table Energy Energy Bohr Binding
Material Classification (eV) (nm) Radius Energy
(nm) (meV)
CdS II-VI 2.42 512 2.8 29
CdSe II-VI 1.76 705 4.9 16
GaN III-V 3.42 360 2.8
GaP III-V 2.26 550 10-6.5 13-20
InP III-V 1.35 920 11.3 5.1
GaAs III-V 1.42 870 12.5 5
AlAs III-V 2.16 570 4.2 17
Si IV 1.11 1150 4.3 15
Ge IV 0.66 1880 25 3.6

In bulk semiconductor materials, the energy levels of both conduction band and
valence band are continuous, with electrons and holes moving freely in all
directions. As the dimensions of the material shrink, effect of quantum
confinement will easily be seen.

Three different types of confinement that have been realized among

inorganic semiconductors are described below and shown in figure (1-3).
One dimension confinement (quantum well)
Two dimension confinement (quantum wire)
Three dimension confinement (quantum dot)
 Bulk quantum well quantum wire quantum dot
Fig(1-3) types of electron confinement[29]

A brief description of the above low dimension confinements is given below:

1.7 Types of Confinement in Semiconductors

1.7.1 one – dimension confinement (quantum well) (q.w)

In this system the electrons are free to move in two dimensions but their
motion are confined in the direction perpendicular to the free planes. Quantum
well is a sandwich structure with a thin layer of narrower band gap
semiconductor in the middle of two layers of wider band gap semiconductor.
There are two types of quantum wells. In a type I quantum well, a potential well,
which confines the electrons and the holes in the narrower band gap material
region, is formed between the narrower and wider band gap materials; while in a
[10]
type II quantum well , the electrons and the holes are confined in different
layers as shown in figure (1-4).
 Fig (1-4) Illustration of type I and II quantum well [10]

In a quantum well, the electrons and the holes can only move freely in
two dimensions. The model of “a particle in a one-dimensional-box” can be
used to provide a first description of the movement of the carriers. In the
semiconductor, unlike the model, the potential barriers are finite and are
determined by the difference in the band gaps of the two semiconductors and
whether the alignment forms a type I or type II quantum well. Because of the
finite value of the potential barrier, the wave functions of electrons and holes do
not have to be zero at the boundaries. The wave functions extend into the wider
band gap material, where they decay exponentially into this region. Also, the
lowest energy band-to-band optical transition is not equal to the band gap of
smaller band gap semiconductor. It is at a higher energy level determined by the
difference between the lowest state of the electrons in the conduction band and
the corresponding state of the holes in valence band [10]. For electrons, the lowest
energy level in a square potential well can be calculated as

h2 j 2
E j  Ec  ....................1  1
8m  d 2
Where j is the quantum number labeling the level
d is the width of the potential well
m* is the effective mass

The electron-hole coulomb potential in quantum well is give by [10].

e2 1
V ( x, y)   ....................1  2

x2  y2

For confinement along the Z-direction.

ε is the material permittivity.
e is the electron charge
The exciton binding energy is increased due to spatial reduction, and the
effective Bohr radius aB(q.w) of the exciton in quantum well is half of it's value
in bulk aB(bulk).

1
a B (q.w)  a B (bulk ).......................1  3
2

Where a B (bulk )  ....................1  4
 * e2

me* .mh*
Where μ* is the electron –hole reduced mass =
me*  mh*

1.7.2 Two – dimension confinement (quantum wire) (q.wire)

In this configuration the electron motion are confined in two directions
and allowed only along the wire axis, as shown in figure (1-3) .The coulomb
potential is [10]
e2
V ( x)   ....................1  5
x
The attraction force between the electron and hole in quantum wire is stronger
than in bulk or in the quantum well.

1.7.3 Three – dimension confinement (quantum dot) (q.dot)

In this system the carriers are confined in all directions in quantum box or
quantum dot [29] as in figure (1-3). Depending on the ratio of confinement length
d to the Bohr radius (d/aB) of the exciton in bulk there are two distinct regimes,
namely:
The exciton confinement regime and charge carries confinement regime.
d
When 1 the motion of exciton is not confined due to boundary conditions.
aB

d
When 1 , The number excitons or bound states is formed because the
aB

kinetic energies of the electron and the hole are larger than the Coloumb energy
[33]
.The wave function is squeezed due to strong confinement and the electron
and the hole individually occupy the lowest energy state in a confined
potential[1]. The dimension of a quantum dot is smaller than the De Broglie
wavelength of thermal electrons, which is[34]
h h h
    7.6nm
 2me E 
1
2 2me KT 
1
2

An important property of a quantum dot is its large surface to volume ratio. The
consequence of this feature is that quantum dots have pronounced surface-
related phenomena [34].
Consequences of Nanodimension:
1.8 Density of states

The density of states in three dimension crystal is found from the energy
momentum relation (E-k) which is simple parabolic from in crystal;
 2 2
E k ............................1  6
2m 
The density of state is the number of available electronic state per unit volume
per unit energy around an energy E as shown in figure (1-5).

Fig(1-5): The density of states in different confinement[29]

An electron near the conduction band edge may be approximately

described as a particle of mass me confined to three dimension cubic box (of
dimension d with perfectly reflecting wall), i.e. a three dimension infinite
rectangular potential well. The standing wave solutions required that the
Components of the wave vector k (k x , k y , k z ) are discrete values
q1 q 2 q3
k ( , , ) and the modes number q1,q2,q3 are positive integers and d is
d d d
the confined width. The tip of the vector k must lie on the points of lattice
 
whose cubic unit cell has dimension of . Thus there are ( ) 3 points per unit
d d
volume in k - space. The number of states whose wave vector k have
magnitudes between k and 0 is determined by counting the number of points
lying within the positive octant of sphere of radius k (with volume
4 k 3 k 3
( )  ). Because of spin, each point in k - space correspond to two
3 2 6

 k 3 
2   
    k  3
3
6
states. There are approximately  3 2 d points in the volume d 3
 
3
 
 
d 

 k3 
and   points per unit volume. It follows that the number of states with
 3
2


electron wave number between k and k+∆k per unit volume is.

 d  k 3   2
 k k     k   k k ............................1  7
 dk  3 2   2 
 

So the density of states is :

k2
 k   .............................1  8 .
2
If  E E represents the number of conduction band energy levels ( per unit
volume ) lying between E and E+∆E , then , because of one-to-one
correspondence between E and k given by equation (1-9) the densities  E  and
 k  must be related by

 E dE   k .dk............................1  9

 k 
  E   ..............................1  10
 dE 
 
 dk 

2m  2
1
2 2
Since E k ..........1  6  k E ..............1  11
2m  

dE  2
  k ......................1  12
dk m 
Sub studies eq. 1-8 and eq. 1-12 in eq. 1-10 , we can get
k2  2 k .m 
Thus  E    ....................1  13
 2 .k  2 2
m
Sub studies eq. 1-11 in eq. 1-13 the  E  is write as follows :-

2k .m  2m  2
3

  E    E ...................1  14
2 2  2 2 2  3
This is in case of the bulk [10].
For one dimension confinements in d1 (quantum well)

 k  
k
the density of states per unit area in (y-z) plane and therefore


 k  
k
.............1  15
 .d1

The density of states per unit volume from eq (1-10)

 2 .k 2
using E  Ec  Eq1  ............................1  16
2m 
Where Ec is the Coulomb interaction energy between the electron and hole.
dE  2
  k
dk m 

k
 .d m
And  E   2 1  .................................1  17
  . 2 d1
k
m
This is independent of E.
In case of 2-dimensional confinements in d1 and d2 (quantum wire).
the density of states per unit volume :
1
2.m 
1
2
 E  
1
. E 2 ..............................1  18
d1 d 2  .

In quantum dot the allowed energy levels are discrete and well separated so that
the density of states is represented by a sequence of impulse function at the
allowed energies.
 
 E   2  E  Eq  Eq  Eq ................................1  19
x y z

qx qy qz

Where Eq , Eq and E q are quantized electronic states

x y z

given by:
 2 q1 d1 2
Eq x 
2m 

 2 q 2 d 2 
2

Eq y  ...................1  20
2m 

q3 d 3 
2

Eqz 
2m 

The band gap energy momentum relation is

 2 k12  2 k 22  2 k 32
E  Ec    ..............1  21
2mc 2mc 2mc

q1 q 2 q3
Where k1  , k2  , k3 
d1 d2 d3

q1 , q2 , q3 ......................  1,2,3................

In quantum well, since d1<<d2 , d3 ,k1 takes on well separated discrete values ,
where as k2 and k3 have close spaced discrete values which may be
approximated as a continuum . Thus (E-k) relation for quantum wells is
 2k 2
E  Ec  E q1  ...........................1  16
2m 
Where k is the magnitude of two –dimension k k 2 , k 3  vector in (y-z) plane .
In case of quantum dot where the electron is confined in x , y , z direction the
E-k relation can be written as :
E  Ec  Eq1  Eq 2  Eq3 .............................1  22
 2
q 
  1 2

Where E q1   1 
d
,
2me
2
q  
  2
2

  2 
d
E q2
2me
2
q  
  3
2

E q3   3 
d
and
2me

The allowed energy levels are discrete and well separated so that the density of
states is represented by impulse function (data function).
These results show that the band gap up shift is related to the quantum dot size
which can be written as [10] [35] [36] [37]:
 2 2
E (eV )  ..............................1  23
2m  e d 2

ΔE = Egdot - Egbulk
Where Egdot is quantum dot band gap
Egbulk is bulk band gap
m* b is effective mass for crystal
e is charge electron
d is radius of quantum dot

1.9 The applications of the quantum dots

Quantum dots are particularly significant for optical applications due to
their theoretically high quantum yield. In electronic applications they have been
proven to operate like a single-electron transistor and show the Coulomb
blockade effect. Quantum dots have also been suggested as implementations of
qubits for quantum information processing.
The ability to tune the size of quantum dots is advantageous for many
applications. For instance, larger quantum dots have spectra shifted towards the
red compared to smaller dots, and exhibit less pronounced quantum properties.
Conversely the smaller particles allow one to take advantage of quantum
properties.

Being zero dimensional, quantum dots have a sharper density of states than
higher-dimensional structures. As a result, they have superior transport and
optical properties, and are being researched for use in diode lasers, amplifiers,
and biological sensors. High-quality quantum dots are well suited for optical
encoding and multiplexing applications due to their broad excitation profiles and
narrow/symmetric emission spectra. The new generations of quantum dots have
far- reaching potential for the study of intracellular processes at the single-
molecule level, high-resolution cellular imaging, long-term in vivo observation
of cell trafficking, tumor targeting, and diagnostics.

1.9.1 Applications engineering

Prior to the introduction of the quantum dot, microelectronic technology

has focused on reducing the size of transistors to produce increasingly smaller,
faster and more efficient computers (Shrinking Information Storage to the
Molecular Level). However, this method is reaching its physical limit due to the
restrictions placed by the laws of physics that do not allow these devices to
operate below a certain size. With this advantageous feature of quantum dots,
information storage can be brought down to the molecular level. Since no flow
of electrons to transmit a signal is needed, electric current does not need to be
produced and heat problems are avoided. Also, the quantum dot
devices are sensitive enough to and can make a usage
of the charges of single electrons. With improvements in
quantum dot ordering and positioning [38].
 The color of the emitted light depends on the size of the dots: the larger
the dot, the redder the light. As the dots shrink in size, the emitted light becomes
shorter in wavelength, moving toward the blue. A rainbow of colors can be
emitted from a single material simply by changing the dot size, therefore use for
quantum dot LEDs is to emit white light for uses in laptop computers or as
internal lighting for buildings or cars [39].
Quantum dots also have other applications like quantum dot lasers which
promises far more great advantages than quantum well lasers. Because quantum
dot lasers are less temperature-dependent and less likely to degrade under
elevated temperature, it allows more flexibility for lasers to operate more
efficiently. Other beneficial features of quantum dot lasers include low threshold
currents, higher power, and great stability compared to the restrained
performance of the conventional lasers. Respectively, the quantum dot laser will
play a significant role in optical data communications and optical networks [38].
Optical switches have been a major research objective in the scientific
community. The use of optical switches would increase the rate at which data
can be transferred. With regular switches, data can only travel as fast as the
electrical current can, but optical switches can travel almost as fast as the speed
of light. The principle of optical switches is that semi-conductors will only allow
certain levels of energy to pass through it. So if we place a quantum dot semi-
conductor in a circuit, but supply a voltage below the acceptable range, current
will not flow. However, if we shine a light on the quantum dot semi-conductor,
it would put enough energy into the semi-conductor that it will allow current to
flow. This idea is mainly for powering electronic devices, but using quantum-
dots as receivers for electrical data is just a step up [38] .
1.9.2 Applications Biology

In modern biological analysis, various kinds of organic dyes are used.

However, with each passing year, more flexibility is being required of these
dyes, and the traditional dyes are often unable to meet the expectations. To this
end, quantum dots have quickly filled in the role, being found to be superior to
traditional organic dyes on several counts, one of the most immediately obvious
being brightness (owing to the high quantum yield) as well as their stability
(much less photodestruction). For single-particle tracking, the irregular blinking
of quantum dots is a minor drawback.

The use of quantum dots for highly sensitive cellular imaging has seen major
advances over the past decade. The improved photostability of quantum dots for
example, allows the acquisition of many consecutive focal-plane images that can
be reconstructed into a high resolution three dimensional image. Another
application that takes advantage of the extraordinary photostability of quantum
dot probes is the real time tracking of molecules and cells over extended periods
of time. Researchers were able to observe quantum dots in lymph
nodes of mice [40].

Scientists have proven that quantum dots are dramatically better than existing
methods for delivering a gene-silencing tool, known as siRNA, into cells.[41]

Semiconductor quantum dots are nanoparticles that have attracted

widespread interest in biology and medicine due to their unique optical and
electronic properties. These properties, especially their reduced tendency to
photobleach and the dependence of their fluorescence wavelength on their size,
make them suitable for fluorescent probing applications to detect and medication
cancer biomarkers in vitro and in vivo in cells/tissues/whole body. There is
considerable interest among researchers due to the recent developments in
quantum dot technology. Quantum dots have been encapsulated in amphiphilic
polymers and bound to tumor-targeting ligands and drug delivery vesicles for
targeting, imaging and treating tumor cells. Present efforts are focused on
exploring the massive multiplexing capabilities of the quantum dots for the
simultaneous detection of multiple cancer biomarkers in blood assays and cancer
tissue biopsies. These advances in the quantum dot technology have unraveled a
great deal of information about the molecular events in tumor cells and early
diagnosis of cancer [42].
Now researchers are able to see the minute-by-minute activities of cancer
cells, thanks to a new technology that uses fluorescent quantum dot [42]. Shown
that in figure (1-7).

Fig (1-6) multicolor quantum dot probes injected into a mouse can

detect and track multiple tumor targets[42].

First attempts have been made in using quantum dots for tumor of cancerous
targeting under in vivo conditions. There exist two basic targeting schemes:
active targeting and passive targeting. In the case of active targeting, quantum
dots are functionalized with tumor specific binding sites to specifically bind to
cancerous cells. Passive targeting utilizes enhanced permeation and retention of
tumor cells for the delivery of quantum dot probes. Fast growing cancerous cells
typically have more permeable membranes than healthy cells, allowing the
leakage of small nanoparticles into the cell body. Moreover, cancerous cells lack
an effective lymphatic drainage system, which leads to subsequent nanoparticle
accumulation [42].

Another cutting edge application of quantum dots is also being researched as

potential inorganic fluorophore for intra-operative detection of tumors using
fluorescence spectroscopy.

Though QDs are still under research for other possible applications and need
more technological advancement in order to be put into use, the features
introduced will grant far better optical communication, significant change in
electronic devices, and even detection of antigens in the body tissues.

2.1 Introduction:
This chapter presents the description of two methods were implemented
in our research for preparation of CdS quantum dot. The first one is the chemical
spray pyrolysis method, whereas the Second is the colloidal CdS quantum dot
preparation method.
The testing for CdS quantum dot is as follow is described as well by
studying the optical properties from the measurements of the absorption
spectrum of the in order to calculate the energy gap of the formed quantum dots
and the crystal size. Whereas the Second is the emission spectrum was measured
hence the energy gap and crystal size were also calculated. Finally we study the
samples examination by using optical microscope (visible and UV lamp) and
transmission electron microscope.
X-ray diffraction is used in our work to study the structures and calculated the
crystal size of the samples were prepared by two methods.
2.2 The chemical spray pyrolysis method for preparation CdS
quantum dot.

2.2.1: The chemical spray pyrolysis system:

Figure (2-1) represents the setup of the thermal chemical spray pyrolysis system.

Fig(2-1) Chemical spray pyrolysis system setup

The parts of the thermal chemical spray pyrolysis system are as follow.
a- Glass atomizer.
The glass atomizer consists at a top of a spray solution container.
The container of spray solution is ended by glass capillary tube surrounded by a
bubble tube, which is connected by electro mechanical valve to control the
flowing gas under pressure between (0.75-1) bar.
The dimensions and shape of this atomizer is shown in figure (2-2).
 Fig (2-2) Diagram of the atomizer

b- The heater:
It is a hot plate electrical heater with temperature controller. The
temperature is registered by digital read out, the rang of the heater temperature
was (1- 400) °C with accuracy of  l°C.
In this work, the heater was set at 400°C and the shot was limited by controlling
the (on- off) time periods by the controller unit.
C- The flash gas
The flash gas used for atomization was Nitrogen gas. The Nitrogen
cylinder was connected to the atomizer through a solenoid valve. It's (on- off)
time was controlled by a timer as shown in figure (2-3)

Fig(2-3) The controller circuit for chemical spray pyrolysis

2.2.2 Preparation of the spray solution

The spray solution used for preparation of CdS quantum dot was prepared
by mixing aqueous cadmium chloride solution (cadmium chloride is a white
crystal, of molecular structure CdCl2 2H2O, and molecular weight equal to
219.34 with purity 99.5% supplied by Fluka company) with aqueous thiourea
solution (thiourea is white crystal, of molecular structure CS(NH2)2, and
molecular weight of 76.12 with purity 99.8% supplied by Fluka company).
Aqueous cadmium chloride solution was prepared (0.1 and 0.5) M by
dissolving (0.1 and 0.5) mole cadmium chloride in one liter of distilled water, in
this case the aqueous cadmium chloride solution is the source for the cadmium
ions (Cd) +2.
Aqueous thiourea solution (0.1 and 0.5) M was prepared by dissolving
(0.1, 0.5) mole in one liter of distilled water in which the aqueous thiourea
solution is a source for sulfide ions (S-2).
The formula used for Molarity calculation is :
mole wt
M  .............................2  1
volum(liter ) M .wt  V

The unit of molarity is mole/ liter.

The spray solution which is used for spray process was obtained by
mixing 1:1 CdCl2 solution and CS (NH2)2 solutions. Two methods were used to
prepare CdS from the above mixtures of CdCl2 and CS (NH2)2 solutions.
Either by sudden heating of the mixed solution or by making the solution alkali,
these methods produce (yellow-orange) precipitates of CdS, used in this work
for preparation CdS quantum dot.

2.2.3 Substrate preparation for spray

The substrate was cleaned before using for precipitation process by water
and soap then washing with distilled water using ultra sonic for 30 min, then
drying the substrate in oven at 50°C for 25 min after that cleaning the substrate
using alcohol and then dries at the same temperature.
Some of the cleaned substrates were used to obtain defectives of
nanometer dimensions, some of them were left in air for 48 hours in order that
the dust can be adsorbed on the surface. Another substrates were sooted with
Lanthanum Oxide in order to obtain a crystal structure in nanometer
(Lanthanum Oxide is white crystal of molecular structure La2O3 and purity
99.99%, supplied by Nanoamor Company,), in order to obtain a glass slide with
nanometer defects.
2.2.4 Synthesis of CdS film
Semiconductor CdS film was prepared in order to compare it with CdS
film which was prepared by chemical spray pyrolysis method, the using the
following procedures.
The substrate was heated by electrical heater at 400°C and keeping the
temperature at 400°C by using thermocouple and control devices. After that the
prepared mixture (CdCl2 + CS (NH2)) was spray for 3 sec an the heated
substrate leaving the sample for 12 sec, and again heated for 400°C for
homogenizing the film.
The controlling of the spray process was through a controlling of the
solenoid valve by timer circuit as shown in figure (2-3)
The reaction of the spray chemicals on the heated substrate is yielding for
the following reaction.


CdCl 2  H 2O  CS ( NH 2 )  H 2O  CdS   H 2 S  Cl 2  H 2O  NH 3  CO2 [43]
precepitat gas gas vapour gas gas

…………......2-1
During the chemical reaction many gases like H2S, Cl2, NH3 and CO2, also
vapor water was obtained from this reaction due to a high temperature of the
substrate. At the end of the reaction a (yellow-orange) precipitate remain from
the reaction which is very thin film of CdS form.

There are several experimental parameters which control the homogenize

of the film and its thickness. These are the spraying time, the height of the
atomizer and the pressure of the nitrogen gas.

From the preparing experiments it was found that the 3 sec spraying time
and 30 cm high of the atomizer is a suitable condition to obtain a very thin CdS
film. [This is the condition of preparing homogeneous thin CdS film at 400°C
substrate temperature.

The X- ray diffraction was used for testing the prepared CdS semiconductor
film. A conventional method was used for measuring tha thickness of the film
by using the electronic balance (Sartorius- Germany) following the equation:

weight of specimen after spray - weight of specimen before sprey

Film thickness 
density of spray matrial  area

We found that the thickness of the film was 500nm.

2.2.5 Synthesis of CdS quantum dot

Two methods were used for synthesis of CdS quantum dot by the
chemical spray pyrolysis:
a- The CdS quantum dot can be constructed by spray the mixture of CdCl 2
solution and CS(NH2)2 solution on a glass slides containing nanometer defects.
We can notice the nanometer defects on the glass slides by optical microscope
as show in figures (2- 4a) and figure (2-4b).

Fig (2-4a) defected by dust Fig (2-4b) defected by La2O3

The scale of the image is 10μm
The substrate which contains nanometer defects was heated at fixed temperature
of 400oC for 10 min, and then the substrate becomes ready for spray process
sprayed for 3 sec. And the reaction (2-1) occurs on nanometer defects at 400oC
and the CdS quantum dot formed on nanometer defects.

b- The second method was used for synthesis of CdS quantum dot by addition
of approximately 20μg of (La2O3) to 20ml of a mixture of aqueous cadmium
chloride solution and aqueous thiourea solution. The above mixture was mixed
for 10min by the stirrer in order to homogenize the (La 2O3) in the mixture and
prevent the coagulation. The substrate after cleaning was heated to 400 oC as
mentioned before for 10 min and becomes ready for spray process.
The reaction occur as (2-1) on glass slides after spring the mixture for
3 sec also the reaction formed on La2O3 crystals after exposure to temperature
the CdS quantum dot formed on La2O3 crystals.
From this experiment we found that La2O3 can not react or dissolve in the
mixture and does not effected by temperature

2.3 Synthesis of colloidal CdS quantum dot

Two chemical methods were used to prepare CdS quantum dot as a liquid
or as a colloidal. The first by using nanoparticles and the second using
compounds to reduce the surface tension during the reaction such as a surfactant
which reduces the surface tension of the solvent or as a copping agent.
The following explanations apply for the system used for both methods:
2.3.1 System for colloidal CdS quantum dot preparation
a- Three necked round bottle flask was used for the reaction: one neck for argon
gas in put and the other for the gas out put, and the middle neck for
thermometer, and for adding the reacting compound.
b- Hot plate heater with magnetic stirrer was used for homogenizing the
materials.
c- Cylinder for argon gas was used to flow argon gas through the reaction flask
to expel the oxygen and to prevent oxide formation (see figure (2-5)).

Fig. (2-5) System for colloidal CdS quantum dot preparation

 2.3.2 Synthesis of colloidal CdS quantum dot by using
nanoparticles
This method is very simple in which the reaction takes place on
nanoparticles between aqueous cadmium chloride solution, which is the source
for Cd+2 ions and aqueous thiourea solution which is the source for S-2 ions.

The explanation of the method is as follows:

A mixture of 10ml of CdCl2 solution (0.1M) and 10ml of CS(NH2)2
solution (0.1M), and then 0.05gm of La2O3 as nanoparticles was added to the
mixture and mixed for 10 min by the magnetic stirrer.
The advantage of mixing is to prevent the coagulation and to get
homogeneous diffusion of La2O3 in the solution.
After that the mixture was added to the glass flask and closed with stopper
then argon gas was purged in order to homogenize the diffusion of La2O3.
After that 3ml of Ammonia solution was added slowly while the magnetic
stirrer was mixing the solution and then the reaction becomes alkaline and the
reaction is:

CdCl 2  H 2O  CS ( NH 2 )  NH 4OH  CdS   NH 4Cl   H 2 S  Cl 2  NH 3  CO2

precepitat gas gas gas gas

.............2  2

The La2O3 can not share the reaction but only to be bases for CdS crystal
formation.
From the above reaction the CdS is formed and the presence of La2O3
particles as nanostructure, the CdS can be distributed on the (La2O3) particles
and the synthesis of CdS of nanometer structure which is known as CdS
quantum dot.
The (yellow-orange) precipitation was formed and separated using
centrifugation instrument.
 The advantage at the precipitation separation form the solvent is to step
the reaction, since the crystal size formed depend on the time of reaction (time
of crystal synthesis) [19].
The CdS quantum dot formed can not be very pure because it contains
NH4Cl- compound. In order to eliminate the NH4Cl- compound the mixture was
washed with distilled water where CdS is insoluble in water while NH4Cl- was
very soluble.
This method for purification was repeated 5 times. For testing the washing
method AgNO3 solution was added and the AgCl was then formed as a
precipitate as given in the following equation:

NH 4Cl   AgNO3  AgCl   NH 4OH...............................2  3

This means that NH4Cl- still presents with CdS quantum dot and therefore, more
washing was needed.
Taken the precipitation of CdS quantum dot was grinded and analyzed with
X–ray diffraction to identify the crystal structure. To study the absorption and
fluorescence of CdS quantum dot the material was dissolved in hexane as a
solvent.

The above mentioned procedure was repeated while heating the mixture
of aqueous cadmium chloride solution and aqueous thiourea solution and
Lanthanum oxide to 90ºC. Then ammonia solution (NH 4OH) was added slowly
with stirrering. The mixture stirrering and heating was continued for 3hr until
drying of the mixture was obtained. The product was yellow –orange powder
which is CdS quantum dot. The powder then dissolved in water, dried, grained
and then purified as mentioned before and then X-ray diffraction was recorded
and the optical properties were then tested.
2.3.3 Second method for Synthesis of colloidal CdS quantum dot
The CdS quantum dot was prepared as a colloidal form reaction of
cadmium chloride solution and oleylamine (Cd –oleylamine complex) with
sulfite oleylamine(S- oleylamine).

The explanation of the method is as follows debutante preparation of solution:

Cd-oleylamine complex was prepared (0.15M) by adding 1.5mmole of cadmium
chloride to 10ml of oleylamine solution (Molecular structure C 18H37N supplied
by Fluka). The mixture was then transferred to the three- necked flask and argon
gas was purged as given before.
The mixture was heated at 90oC with stirring using the magnetic stirrer.
After a complete dissolution of the cadmium chloride in oleylamine solution, the
mixture was left on a magnetic stirrer for 30min of 90 oC, the Cd-oleylamine
complex was formed [24].
S-oleyamine solution was first prepared. The best mole ratio for mixing of
S-oleylamine: Cd-oleylamine was 2:1. Which is the same ratio used by Ken-Tye
Yong et al researchers [12]. The molarity of S- oleylamine solution opposite to
0.15M of a Cd–oleylamine complex is 0.15M. The mole ratio was used is the
same ratio used by the researchers.
The S- oleylamine of concentration 0.15M was prepared by adding
0.75mmole of sulfur to 5ml of oleylamine solution. The mixture was mixed by
magnetic stirrer until a complete dissolution, and the colour of the solution was
changed from yellow to red, this means that the S- oleylamine was formed.
2.3.4 Synthesis of colloidal CdS quantum dot
The colloidal CdS quantum dot was prepared by reaction of S- oleylamine
solution with Cd- oleylamine complexes. The mole ratio 2:1 was used, and the
variation in the mole ratio leads to change in time of formation of dot.
Therefore, the time taken is about 6 hours for the mole ratio 2:1 of CdS quantum
dot formation as given in the literature [12]:

The Cd- oleylamine complexes solution were heated at 170oC for 20 min
under argon flow, and S- oleylamine solution was injected under gentle stirring
into the hot reaction mixture.
The reaction mixture was held at 170 oC and stirred for 6h, and then
aliquot was removed by a syringe and injected into large volume of ethanol at
room temperature to quench the reaction. The yellow precipitate of CdS
quantum dot formed can be separated by centrifugation.
The yellow precipitate at CdS quantum dot was formed and the precipitate
was dissolved in cyclohexane, toluene, and hexane solvents and tested by
emission and absorption spectrum methods also the image was taken by electron
microscope for CdS quantum dot before the dissolution process.

2.4 Optical Properties

The optical properties of the prepared CdS quantum dot were measured.
The absorbance of the samples was measured using:
LABOMED.INC spectra UV/Vis Double Beam pcscanning, covering range
from (190 – 1100) nm as shown in figure (2-6). The scanning range of the CdS
quantum dot absorption was (200-600) nm using glass substrate as a reference
sample. This was for chemical spray pyrolysis method while for
CdS quantum dot preparation by chemical methods, the reference samples were
the solvents used to dissolve CdS quantum dot.
 The fluorescence spectrum was measured using (VARIAN fluorescence
spectrophotometer, supplied by Eclipse Company) with the spectrum range from
(190-1100) nm) as shown in figure (2-7). The scanning range of CdS quantum
dot emission was (400-600) nm.

Fig (2-6) the absorption spectrophotometer

Fig (2-7) the fluorescence spectrophotometer

The measured absorbance as a function of wavelength was used for

calculation of several parameters of the CdS quantum dot such as: absorption
coefficient (α), optical energy gap (Eg) and the size of quantum dot.

The absorbance of the bulk semiconductor was found to be greater than

that of quantum dot as observed in a previous study [30].
 The optical energy gap can be calculated by calculate the absorption
coefficient (α) which depend on the film thickness
( length of the absorption media ) and absorbance, as given in the equation:

α = 2.303 ( ............................2-2
Where A is absorbance, and d is thickness. From the relation between (αhυ)2 as
a function of the photo energy , we determined the energy gap using the value
(αhυ)2 = 0 from the extrapolation, and applying the relation:

αhυ = B(hυ - Eg)r ……………………..2-3

Where B is constant, r is a parameter that has different values (1/2, 1, 3/2, 2) [29].
And the crystal size or quantum dot size (diameter) was then calculated from
energy gap using equation (1-23).
The energy gap and crystal size were calculated from emission spectrum .

2.5 CdS quantum dot morphology study

a- An optical microscope supplied with digital camera was used to take photo
graphs for the samples on the glass substrate the samples were irradiated with
(UV and Vis) sources in a dark room to increase the visibility. The used
optical microscope is shown in Figure (2-8).
 Fig (2-8) the optical microscope

b- A Transmission Electron microscope, shown in figure (2-9), was used to

study the diameter of dot formed and to show the quantum dot distributed
inside of the specimen.

Fig (2-9) the Transmission Electron microscope

2.6 X – Ray diffraction study
To study the CdS quantum dot crystal structure prepared by different
methods, X–ray diffraction spectrum method was used using (XRD -6000 Labx,
supplied by Shimadzu, X-ray source is Cu) as X–ray instrument.

X-ray is a widely used method to determine the dimensional parameters for

crystals and nowadays for the estimation of quantum dot size. For this purpose
the following equation, known as the Scherrer equation is used [44]:
0.9
d ..............................2  4
B cos 

d is the quantum dot size.

λ is the wavelength for X-ray source ( X-ray source is Cu with λ=1.5406 A°).
B is the full width at half maximum FWHM.
θ is the diffraction angle.

3.5 Conclusion
We could draw from this work the following conclusion:-

1- Synthesis of CdS quantum dot by spray the mixture of CdCl 2 solution and
CS(NH2)2 on glass slides containing nanoparticle, Where I noticed both of
nanoparticle (La2O3 and dust ) to lead Synthesis CdS quantum dot ,
namely Its' not necessary these nanoparticle to be nanostructure in order
to synthesis quantum dot , The size is enough to be in nanometer unit.
2- No synthesis of CdS quantum dot from mixed CdCl2 solution, CS(NH2)2
solution, NH4OH solution and La2O3 nanoparticles at room temperature is
produced, but the synthesis occurs when the reaction temperature
 increased to 90°C. Then the reaction heating is necessary for the synthesis
of quantum dot in this method.
3- We obtained different values of CdS quantum dot size, and this provides
many laboratory applications.
4- Formation tats in energy gap (trip stat) when synthesis CdS quantum dot,
for that be using CdS quantum dot to made detector.
5- From optical properties (absorption spectrum) of CdS quantum dot we
noticed narrowed absorption edge instead of broad in CdS bulk. It means
that excess in energy gap consequential decreasing in crystal size.

3.6 Suggestions for Future Work

According to our results, the following conclusions are suggested:-
1- Synthesis of CdS quantum dot and studying its electrical properties.
2- Synthesis of CdS quantum dot and studying its electrical and optical
properties in IR region.

3.1 Introduction
This chapter displays the results and discussion for the measurements
mentioned in the previous chapter.

3.2 Characteristics for CdS film synthesis by chemical spray

pyrolysis

3.2.1 X-Ray Diffraction Results for CdS film

The X-ray diffraction of CdS film prepared by chemical spray pyrolysis
technique on glass substrate, for the film thickness <1 μm, was obtained by two
different concentration (0.1 and 0.5) M. in which the highest intensity appear at
(101) at 2θ equal 28° for concentration 0.5 M.
While other planar gives lower intensities at different angles for the same
concentration (0.5 M) the results obtained from X-ray diffraction indicate a quite
comparable with data in (ASTM) that means the CdS film is a polycrystalline as
shown in figure (3-1) and (3-2) the X-ray diffraction of CdS film prepared by
chemical spray pyrolysis technique on glass substrate.

Fig(3-1): The X-ray diffraction for CdS film of 0.1M concentration

 Fig(3-2): The X-ray diffraction for CdS film of 0.5M concentration

In order to get more evidence about the formation of the CdS films by such
technique, the optical properties were studied.

3.2.2 Optical properties of CdS film

a- Absorption spectrum
This technique was used in order to get more evidence about the
formation of CdS film, the absorption spectrum for CdS film formation at
two concentrations (0.1 and 0.5) M are shown in figure (3-3) and (3-4).

Fig (3-3): The absorption spectrum for CdS film of 0.1M concentration
 Fig (3-4): The absorption spectrum for CdS film of 0.5M concentration

The absorption spectrum shows that the material has an absorption edge
between (400- >500) nm and it is transparent the visible region. These results
are in agreement with the literatures [30] [43].

Calculation of the energy band gap from the absorption spectrum was
carried out using the graphs shown in figures (3-5) and (3-6) using the equation
(2-3). The extrapolation of the liner part of (αhυ)2 vs. photon energy (hυ) gives
energy band gap of about 2.4 eV for two concentrations. This value of energy
gap was quite comparable with value given in the literatures [30] [43].
Fig (3-5): (αhυ) 2 vs. photon energy for CdS film of 0.1M concentration

Fig(3-6): (αhυ)2 vs. photon energy for CdS film of 0.5M concentration
b- Fluorescence spectrum

The fluorescence spectrum of the CdS film is shown in figure (3-7) and
figure (3-8).

Fig(3-7): The fluorescence spectrum for CdS film of 0.1M concentration

Fig(3-8): The fluorescence spectrum for CdS film of 0.5M concentration

Which indicate that the intensity of the fluorescence increase by increasing the
concentration form (0.1 and 0.5) M. The spectrum shows a sharp peak at (500)
nm, while the broad band is due to the aggregation of microcrystalline of the
substrate surface.

3.3 Characteristics of CdS quantum dot synthesis by chemical

spray pyrolysis

3.3.1 morphology study of CdS quantum dot optical microscope.

a- The CdS quantum dot constructed by spray the mixture of CdCl2

solution and CS(NH2)2 solution on a glass slides containing defect nanometer.
In order to apply the chemical spray pyrolysis to produce CdS quantum
dot film, the substrates were defected by nanoparticles. Two types of
nanoparticles were used, the dust nanoparticles and the La2O3 of 15 nm
dimension, as shown in figures (3-9a) and (3-9b).

Fig(3-9a) CdS q.dot on dust Fig(3-9b) CdS q.dot on La2O3

nanoparticles nanoparticles
The scale bar = 10μm

b- The CdS quantum dot constructed by spray for colloidal mixture of

CdCl2 solution and CS(NH2)2 solution and La2O3 nanoparticles on a glass slides
shown in figure (3-9c).
 Fig (3-9c) CdS q.dot constructed by spray the colloidal mixture
The scale bar = 10μm

The interaction due to the sediment CdS carried on the samples and thus
sediment on the nanoparticles. The results show that the separated islands are
formed with microdimension. The photos show aver fine spot of CdS material
are formed, which can be estimated to by in nanodimension , but due the lack in
magnification it can not be measured exactly. We expected that this dots are the
quantum dots.

For more confirmation of the above result, the UV source was used to
illuminate the sample and photographing it by a color digital camera and
analogies the viewed color by the color chart in computer. It was noticed that the
film substrate show a yellow color which represents the CdS background film,
whereas the blue dots represent the quantum dots see figure (3-10a), (3-10b) and
(3-10c).
Fig(3-10a) CdS q.dots on dust Fig(3-10b) CdS q.dots on La2O3
nanoparticles nanoparticles

Fig(3-10c) CdS q.dot constructed by spray the colloidal mixture

The scale bar = 30μm
3.3.2 Optical properties of the quantum dots

a- Absorption spectrum

The absorption spectra for two CdS quantum dot on nanoparticle (dust and
La2O3) are shown in figure (3-11a) and (3-11b).

Fig(3-11a): The absorption spectrum for CdS quantum dots

On dust nanoparticles

Fig(3-11b) The absorption spectrum for CdS quantum dots

on La2O3 nanoparticles
The absorption spectrum for CdS quantum dots, constructed by spray of the
colloidal mixture of CdCl2 solution and CS(NH2)2 solution and La2O3
nanoparticles on a glass, is shown in figure (3-11c).

Fig(3-11c): The absorption spectrum for CdS quantum dots

by sprayed colloidal mixture

The absorption spectrum shows that the material has an absorption edge
between (300- <500) nm. The absorption spectrum features an excitonic peak
around 460nm in figure (3-11a) , 475 nm in figure (3-11b) and 480 nm in figure
(3-11c), but in CdS bulk the excitonic peak is around 510nm. This shift in wave
length is attributed to decrease in the crystal size which confirms the existence
of quantum dot according to equation (1-23). These results are in good
agreement with the results literatures [24][25][35].

The energy gap of the prepared CdS quantum dot on defected substrate
was calculated from the graphic relation between (αhυ) 2 as a function of hυ
using equation (2-3) and figures (3-12a), (3-12b) and (3-12c). The extrapolation
of the linear part of this graph shows that the energy band is higher than that of
solid film. This may be attributed to the formation of CdS quantum dot on the
[35]
nanodefect or due to the improvement of the film quality due to these
nanodefects [12].

Fig(3-12b) (αhυ)2 vs. photon energy for CdS quantum dot on La2O3
nanoparticle

Fig (3-12c) (αhυ)2 vs. photon energy for CdS quantum dot by spray the
colloidal mixture
From above figures the values of energy gap are (2.7, 2.59 and 2.58 eV)
respectively, these values are higher than the energy gap value of CdS bulk. This
extended energy gap may be considered as an indicator for the formation of the
nanocrystalline [45].
The diameter the constructed nanocrystalline could be calculated using the
equation (1-23). We found that the diameter of constructed nanocrystalline
is (5, 6.3 and 6.4) nm respectively and the effective mass of CdS is
(1.82 x 10-31 kg)[45].
The constructed nanocrystal of CdS is a quantum dot because its diameter is less
than 10 nm [45].

b- Fluorescence spectrum
The fluorescence spectra for the CdS quantum dot films prepared on
defected substrates (defected by dust and La2O3) are shown in figure (3-13a) and
figure (3-13b).

Fig(3-13a) The fluorescence spectrum for CdS quantum dot on dust

nanoparticles
 Fig(3-13b) The fluorescence spectrum for CdS quantum dot on La2O3
nanoparticles

The fluorescence spectrum of CdS quantum dot film, prepared by

chemical spray pyrolysis, is shown in figure (3-13c).

Fig (3-13c): The fluorescence spectrum for CdS quantum dot prepared by
spray the colloidal mixture
 The spectrum shows two peaks: the first one is due to bond edge emission
which is centered between ( 460-480 nm), while the other are centered around
530 nm in case of dust nanoparticles shown figure (3-13a) and around 730 nm
for the La2O3 nanoparticles . The first peak is due to broad edge in both spectra,
while the peak around 730 nm for the La2O3 is due to nanostructure surface. The
structure produces surface states in the band gap .and it is noticed in may
nanostructured [46].

The surface state which is some times called triplet state is formed in the
energy gap of the nanostructured films. Its position depends on the electron
concentration which depends on the size of the nanocrystalline [47].
The two graphs (3-13a, 3-13b) indicate that the size of nanocrystals
depends on the defect size on the substrates.
The energy gap from the fluorescence spectrum of the CdS quantum dot were
calculated by using the equation following:-
1240
Eg (eV )  .............................3  1
 (nm)
Fluorescence wavelength are equal to (431, 486 and 478) nm indicating a band
gap are equal to (2.8, 2.55 and 2.59) eV respectively.
Then the diameter for the corresponding CdS quantum dots yield are (4.34, 7
and 6.3) nm.
3.4 Characteristics for colloidal of CdS quantum dot.

3.4.1 X-Ray Diffraction Results for CdS

Two chemical methods were used to prepare colloidal CdS quantum dot.
a- The first method is by using the nanoparticles
The X-ray diffraction of the yield at room temperature formed by
colloidal synthesis is shown in figure (3-14a). and where the reaction time is 3
hours.

Fig(3-14a): The X-ray diffraction for the yield at room temp.

The reaction time is 3 hours

The highest intensity for two different plan (110) and <220> for different,
zinc-blende and wurtzite lattice structure at the same 2θ which is equal to 43°.
When the reaction time is 6 hours the X-ray diffraction of the yield is shown in
figure (3-14b).

Fig(3-14b): The X-ray diffraction for the yield at room temp.

The reaction time is 6 hours

It can be noticed from the figure that there is no indication about the
formation of the quantum dots. This is because the spectrum shows a single
peak. Where as the quantum dot formation shows a polycrystalline structure.
The lack in formation of the quantum dots may be attributing to the aggregation
of the nanocrystals at room temperature or the reaction is not able to form the
quantum dots at this temperature.
When the reaction temperature increased to 90°C, the X-ray spectrum is shown
in figure (3-15a).

Fig(3-15a): The X-ray diffraction for the yield at 90°C.

The reaction time is 3 hours

b- Second method using compounds to reduce the surface tension

Synthesis of CdS quantum dot is by using compounds that reduce the
surface tension during the reaction (oleylamine). The X-ray spectrum is shown
in figure (3-15b), for the samples obtained using this method.
 Fig(3-15b): The X-ray diffraction for yield by using oleylamine

The X-ray diffraction peaks show that the CdS is formed as compared with
the previous X-ray study of the bulk CdS material. The X-ray diffraction for the
colloidal shows that X-ray peaks were broad and this result is in good agreement
with previous studies [9][12][15][24][45], which gives an evidence of the nanostructure
formation. This is because the full width at half maximum (FWHM) of the X-
ray diffraction peaks which has a relation with quantum dot size through
Scherrer equation (2-4).
 From these relations one can calculate the quantum dot size. The results are
listed in Table (3-1).
Table (3-1) summary of parameters of X-ray diff. and crystal size.
Type of CdS structure 2θ(degree) FWHM hkl Size(nm)
CdS Bulk 24.876 0.14390 100 56.56
26.5659 0.21340 002 38.27
28.2448 0.1624 101 50.4
36.6808 0.1597 102 52.43
43.7608 0.1528 110 56.06
47.9212 0.1726 103 50.39
CdS q.dot on
nanoparticle at room 43.7608 0.1872 110 45.68
temp.
CdS q.dot on
25.1 1 100 8.10
nanoparticle at 90°C
26.6981 1 002 8.17
28.4954 1.15 101 7.13
52.0023 1.5 112 5.89
CdS q.dot by oleylamine 25.1508 1.5 100 5.42
26.5483 1.75 002 4.54
27.998 1.75 101 4.68
43.8720 1.1563 110 7.41
47.7793 2.75 103 3.16
52.00 1.375 112 6.43

Eventually the average value of the diameter of quantum dot, synthesized using
nanoparticles at 90°C, is 7.32 nm, and that synthesized using oleylamine is
5.27 nm.
3.4.2 The optical properties

The absorption spectra of the CdS quantum dot in colloidal are shown in
figures (3-16a) and (3-16b).

Fig (3-16a): The absorption spectrum for the CdS quantum dot synthesized
using nanoparticles at 90°C. The reaction time is 3 hours

Fig (3-16b): The absorption spectrum for CdS quantum dot synthesized
by using oleylamine
 It can be noticed from these figures that the material absorbs in the region
(300-500) nm and transmits in the rest of the visible band. This behavior is the
usual characteristics of the CdS material.

The energy gap of prepared CdS quantum dot by chemical methods was
calculated form the graphs between (αhυ) 2 vs. hυ by using the equation (2-3)
see figures (3-17a) and (3-17b).

Fig(3-17a): (αhυ)2 vs. photon energy for the CdS quantum dot synthesized
by using nanoparticles at 90°C. The time reaction is 3 hours

Fig (3-17b): (αhυ)2 vs. photon for CdS quantum dot by using oleylamine
 The values of energy gap calculated from figure (3-17a) and (3-17b) are
equal (2.68 and 2.6) eV indicating a crystal size are (5.38 and 6.47) nm
respectively. These expansions in the energy gap give more evidence for the
formation of the CdS quantum dot in the colloidal synthesis.

The fluorescence spectrum of the quantum dots formed by the colloidal

synthesis is show in figures (3-18a) and (3-18b).

Fig(3-18a): The photoluminescence spectrum for the CdS quantum dot

synthesized by using nanoparticles 90°C. the time reaction is 3 hours
 Fig(3-18b): The photoluminescence spectrum for CdS quantum dot by
using oleylamine

These figures show that the band edge transmission is catered equal (463 and
475) nm indicating an energy gaps of (2.67 and 2.61) eV respectively (using
equation (3-1)). By using equation (1-23) the diameter for CdS quantum dot
yield were (5.49 and 6.29) nm respectively.

There are two peaks around (603 and 676)nm . These two peaks may be
due to the emission from the surface states which are generated by the
nanostructure and established the allowed transition states in the band gap.
 The triplet states are in energy of (2 and 1.83) eV can see that in
figure (3-19).

Fig (3-19) photon excited emission spectra of CdS quantum dot[47]

These two bands are originated from the defect state in the energy band.
These peaks are usually considered as a good indication for the
nanostructure and the quantum dot formation [47].
3.4.3 CdS quantum dot morphology study by transmission
electron microscope
The images of the previous sample were viewed by the transmission
electron microscope (TEM) of (16000, 6200 and 41000) magnifications and
they are shown in figures (3-20a) and (3-20b).

Fig(3-20a): (TEM) images for the CdS quantum dot synthesized by using
nanoparticles at 90°C. the reaction time is 3 hours ,The scale bar ~ 90nm

Fig(3-20b): (TEM) images for CdS quantum dot synthesized using

oleylamine, The scale bar ~ 360nm
 Fig(3-20c): (TEM) images for CdS quantum dot synthesized using
oleylamine, The scale bar ~ 100nm

The photos show that spherical nanocrystals were formed, which is a

good indicator for the formation of the quantum dots in this technique. The
photos also show that some quantum dots are aggregated on the image slide but
the isolated dot has spherical shape and a nanodimension.
 From the previous results and discussion, we can summarize the synthesis
methods and the results in Table (3-2).

Table (3-2) summary of synthesis methods and results

Eg (eV) Size Size (nm)
Synthesis Size(nm) Eg (eV)
from (nm) from X-ray
method from Abs from (PL)
(absorption) from PL diff
chemical
spray
pyrolysis
Defect by
2.59 6.3 2.55 7 -
La2O3
Defect by
2.7 5 2.8 4.34 -
dust
Spray
2.58 6.4 2.59 6.3 -
colloidal
Chemical
method
Using
2.68 5.38 2.67 5.49 7.322
nanoparticle
Using
2.6 6.47 2.61 6.29 5.273
oleylamine
References
1- Massimiliano, Di Ventra Stephane Evoy and James R. Heflin‚ Jr.
"Introduction to Nanoscale Science and Technology" Springer Science and
Business Media, Inc. Boston, p184, (2004).
2- Mark A. Reed, "Quantum Dots", Scientific American January, p118,(1993).
3- Norris, David J, "measurement and assignment of the size-dependent
optical spectrum in cadmium selenide (CdSe) quantum dot" physical Review
B,Vol 53 , no. 24 , pp 16338-16346,(1996).
4- G. A. Stanciu , R. S. Hristu, B. Savu, S.G. Stanciu ," Semiconductor
Quantum Dots Characterization And Applications In Photonics"Excellence
Research as away to E.R.A, Project no. 51,ISSN 1843-5904
5- Kamada Hidehiko," Quantum Mechanical Interference Effects in Single
Quantum Dot Excitons" J.S.T,Vol.57, no.2 pp.101-104, (2002)
6- Sears K., Mokkapati S., Buda M., Tan H. H., Jagadish C. ," In(Ga)As/GaAs
quantum dots for optoelectronic devices" , SPIE, Vol.6415, pp. 641506,
(2007).
7- Ivan A. Dmitriev , Robert A. Suris, " Quantum cascade lasers based on
quantum dot superlattice" physica status solidi a, Vol.202 ,Issue 6 pp.987-
991(2005).
8- Phillip Cervantes, Quentin Williams, Michel Cote, Oleg Zakharov and
Marvin L. Cohen, "Band structure of CdS and CdSe at high pressure",
Am. Phys. Soc.B ,Vol. 54, no. 24, pp. 17 585-17 590 (1996).

9- Yang Li,Eric Chum Yeung Liu,Nigel Pickett J. Skabara, Siobhan S.

Cummins, Stephen Ryley, Andrew J. Sutherland and Paul O'Brien,
"Synthesis and characterization of CdS quantum dots in polystyrene
microbeads" J.Mater.Chem.,vol.15,pp.1238-1243 (2005).
10- Paul Harrison, "Quantum Wells, Wires and Dots: Theoretical and
Computational Physics" John Wiley and Sons, New York (2000).
11- Garnett W. Bryant and Susan Burke," Formation of quantum-dot quantum-
well heteronanostructures with large lattice mismatch: ZnS/CdS/ZnS", J.
Chem. Phys. Vol.114,No.4, pp. 1813 (2001).
12- Ken-Tye Yong, Yudhisthiea Sahoo, Mark T.Swihart, and Paras N.Prasad,"
Shape control of CdS Nanocrystals in One-Pot synthesis " J.Phys.Chem.C
,Vol.111,pp.2447-2458(2007).
13- Omar Manasreh," Semiconductor Heterojunctions and Nanostructures",
McGraw-Hill , (2005).
14- Kapon E., Yun C.P., Harbison J.P., Florez L.T., Stoffel N.G.,
"Low- threshold patterned quantum well lasers grown by molecular beam
epitaxy", ELECTRONICS LETTERS, Vol. 24, Issue 16, pp.985 - 986
(1988).
15- Fuhrmann B., Leipner H. S., Hoche H.R., Schubert L., Werner P. and
Gosele U.," Ordered Arrays of Silicon Nanowires Produced by Nanosphere
Lithography and Molecular Beam Epitaxy", Nano Lett., Vol. 5, No.12,
pp.2524-2527, (2005).
16- Changwu Hu, Jennifer L. Taraci, John Tolle, Matthew R. Bauer, Peter A.
Crozier, Ignatius S. T. Tsong, and John Kouvetakis," Synthesis of Highly
Coherent SiGe and Si4Ge Nanostructures by Molecular Beam Epitaxy of
H3SiGeH3 and Ge(SiH3)4" ,Chem. Mater., Vol. 15, No. 19, (2003).
17- Satoru Tanaka, Sohachi Iwai and Yoshinobu Aoyagi, "Self-assembling GaN
quantum dots on AlxGa1-xN surfaces using a surfactant", Appl. Phys. Lett.
Vol.69, pp.4096-4098,(1996).
18- Tomonori Ishikawa, Tetsuya Nishimura, Shigeru Kohmoto, and Kiyoshi
Asakawa," Site-controlled InAs single quantum-dot structures on GaAs
surfaces patterned by in situ electron-beam lithography", Appl. Phys. Lett.
Vol.76, Issue 2 ,pp.167-172,(2000).
19- C. B. Murray, Shouheng Sun, W. Gaschler, H. Doyle, T. A. Betley, and C.
R. Kagan," Colloidal synthesis of nanocrystals and nanocrystal super
lattices", IBM J. RES. & DEV. Vol. 45, no.1, pp.47-56(2001).
20- Mark C. Barnes, Doh-Y. Kim and Nong M. Hwanga," The mechanism of
gold deposition by thermal evaporation", Journal of Ceramic Processing
Research. Vol.1, no.1, pp.45-52 (2000).
21- P. Nandakumar, C. Vijayan, M. Rajalakshmi, Akhilesh K. Arora and
Y.V.G.S. Murtic," Raman spectra of CdS nanocrystals in Nafion:
longitudinal optical and confined acoustic phonon modes", Physica E,
Vol.11 ,pp. 377-383 (2001).

22- W. William Yu, Lianhua Qu, Wenzhuo Guo, and Xiaogang Peng,
"Experimental Determination of the Extinction Coefficient of CdTe, CdSe,
and CdS Nanocrystals" . Chem. Mater., Vol. 15,pp. 2854-2860(2003).
23- Zhonghua Yu, Jingbo Li, Donald B. O'Connor, Lin-Wang Wang, and Paul
F. Barbara," Large Resonant Stokes Shift in CdS Nanocrystals", J. Phys.
Chem. B Vol. 107,pp. 5670-5674(2003).

24- Jin Joo, Hyon Bin Na, Taekyung Yu, Jung Ho Yu, Young Woon Kim,
Fanxin Wu, Jin Z. Zhang and Taeghwan Hyeon," Generalized and Facile
Synthesis of Semiconducting Metal Sulfide Nanocrystals", J. Am. Chem.
Soc. Vol.125, pp.11100-11105(2003).

25- Yang Li, Eric Chun Yeung Liu, Nigel Pickett, Peter J. Skabara, Siobhan,
Cummins, Stephen Ryley, Andrew J. Sutherland and Paul O'Brien,
"Synthesis and characterization of CdS quantum dots in polystyrene
microbeads" , J. Mater. Chem. Vol.15 ,pp.1238-1243 (2005).
26- Hongwang Zhang, Ken-Tye Yong and Mark T.Swihart, "synthesis of
nanoparticles by spray pyrolysis" Transactions of the Electrochemical
Society,Vol. 2, pp. 249-254 (2006).
27- Hongwang, Zhang and Mark T. Swihart, "Synthesis of Tellurium Dioxide
Nanoparticles by Spray Pyrolysis", Transactions of the Electrochemical
Society, Vol.2, pp. 239-248 (2006).

28- Yang Wu, Gabriel P. Lopez, Larry A. Sklar, Tione Buranda, "Spectroscopic
characterization of streptavidin functionalized quantum dots", Analytical
Biochemistry Vol.364, pp.193-203 (2007).

29- S. M. Sze and Kwok K. Ng," Physics of Semiconductor Devices", Third

Edition, John Wiley and Sons, New York,(2007).
30 - D. Patidar, R. Sharma, N. Jain, T. P. Sharma and N. S. Saxena,
"Optical properties of CdS sintered film" ,Bull. Mater. Sci., Vol.29, No.1,
pp. 21-24,( 2006).
31- R.K. Ahrenkiel, D.H. Levi, S. Johnston, W. Song, D. Mao, and A.
Fischer,"Photoconductive Lifetime of CdS Used in Thin-Film Solar Cells",
IEEE. Issue ISSN: 0160-8371, pp.535 - 538(1997).
32- B. Monemar," fundamental energy gap of GaN from photoluminescence
excitation spectra " phys. Rev. B Vol.10 pp.676-681 (1974).
33- Peter Michler ," Single Quantum Dots Fundamentals, Applications,
and New Concepts", Springer,(2003)
34- Kathleen Meehan , Louis J. Guido , Guoquan Lu , Chris L.Wyatt , Nancy G.
Love. " Synthesis and Characterization of Silica Coated CdSe/CdS
Core/Shell Quantum dots" Dissertation submitted to the faculty of the
Virginia Polytechnic Institute and State University in partial fulfillment of
the requirements for the degree of Doctor of Philosophy In Electrical
Engineering , Blacksburg ,Virginia ,(2005).
35- Jinlong Chen, AiFang Zheng, Yingchun Gao, Chiyang He, Genhua Wu,
Youcun Chen, Xiaoming Kai, Changping Zhu, "Functionalized CdS
quantum dots-based luminescence probe for detection of heavy and
transition metal ions in aqueous solution" , Spectrochimica Acta.part A
Vol. 67 pp.1044-1052 (2008).

36- Y. Wang ,N. Herron ,"nanometer-sized semiconductor clusters: Materials

synthesis, quantum size effects and photophysical properties", J.phys.chem
Vol.95 pp.525-532 (1991).
37- L.E. Brus, "Electron-electron and electron-hole interactions in small
semiconductor crystallites : The size dependence of the lowest excited
electronic state", J.Chem.phys. Vol.80, no.9, pp.4403-4409 (1984).
38- Dr. Kashra Daneshvar " Quantum Dots In a New Light" Optical Engineering
July 16, (2005).
39- Howard Lee "Mighty Small Dots" Lawrence Livermore National Laboratory
(S&TR July/August 2000).
40- Byron Ballou, B. Christoffer Lagerholm, Lauren A. Ernst, Marcel P.
Bruchez, and Alan S. Waggoner " Noninvasive Imaging of Quantum Dots
in Mice" Bioconjugate Chem., Vol.15, pp. 79-86(2004).

41- Maksym V., Yezhelyev, Lifeng Qi, Ruth M. O’Regan, Shuming Nie and
Xiaohu Gao " Proton-Sponge Coated Quantum Dots for siRNA Delivery
and Intracellular Imaging" J. AM. CHEM. SOC. Soc.,Vol.130 (28), pp
9006–9012(2008).

42- Sandeep Kumar Vashist, Rupinder Tewari, Ram Prakash Bajpai, Lalit
Mohan Bharadwaj and Roberto Raiteri " Review of Quantum Dot
 Technologies for Cancer Detection and Treatment" Journal ,
Nanotechnolgy Vol. 2 pp.1-14 (2008).
43- ‫علي فؤاد األمين "دراست الخواص الضوئيت ألغشيت كبريتيدذ الادمدميوو بكبريتيدذ الر دمص الر ي دت‬
‫الايميدمئي الحدرارك "كليدت التربيدت –أبدن الهيد – جممعدت بددذاد‬ ‫بمزيجهمم المحضرة بطري ت الدر‬
)6991(

44- A.L. Patterson "The Scherrer Formula for X-ray Particle size determination
"Physical review Vol.56, pp. 978-982 (1939).

45- S.S Nath, D. Chakar, G.Gope and D. K. Avasthi, " Characterization of CdS
and ZnS quantum dots prepared via a chemical method on SBR Latex" ,
Journal , Nanotechnolgy Vol.4 pp.1-6(2008).
46- Michael A. Stroscio, Mitra Dutta, Babak Kohanpour, Dinakar Ramadurai1,

Dimitri Alexson, Peng Shi, Akil Sethuraman, Yang Li, and Vikas Saini,
"Electrical and Optical Properties of Colloidal Quantum Dots: Role of
Surface States", Departments of Bioengineering, Electrical and Computer
Engineering, and Physics, University of Illinois at Chicago 60607.

47- James W. M. Chon and Min Gu., " Three-photon excited band edge and trap
emission of CdS semiconductor nanocrystals", Appl. Phys. Lett., Vol. 84,
No. 22, pp.4472-4474 ( 2004)

View publication stats