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Theoretical and Experimental Study For (CdSe) Nanoparticles

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Republic of Iraq
Ministry of Higher Education
And Scientific Research
University of Baghdad
College of Science

Theoretical and Experimental Study

For (CdSe) Nanoparticles

A Thesis
Submitted to the council of the College of Science
University of Baghdad
In Partial Fulfillment of the Requirements for
The Degree of Doctor of Philosophy in Physics

By
Hasan Bakheet Jasim

Supervised by

Prof. Dr. Mohammed Taki Hussein Ass. Prof. Dr. Bushra Abbas Hasan

1435 A.H 2014 A.D

1
‫يوسف ‪67/‬‬

‫‪2‬‬
 SUPERVISORS CERTIFICATION

We certify that thesis entitled " Theoretical and Experimental Study For
(CdSe) Nanoparticles " was prepared by Hasan Bakheet Jasim under our
supervision at the Physics Department, College of Science, University of Baghdad
as a partial fulfillment of the requirements for the degree of Doctor of philosophy
in Physics.

Signature:
Name: Prof. Dr.Mohammed Taki Hussein
Address: Physics Department,
College of Science, University of Baghdad
Date: / / 2014
Signature:
Name: : Ass. Prof. Dr. Bushra Abbas Hasan
Address: Physics Department,
College of Science, University of Baghdad
Date: / / 2014

In view of the available recommendations I forward this thesis for debate by the
examining committee.

Signature :
Name: Professor Dr. Raad Abdul kareem Radhi
Address: Chairman of the Physics Department,
College of Science, University of Baghdad
Date: / / 2014

3
 ‫جًٕٓس‪ٚ‬ح انؼـــــشاق‬
‫ٔصاسج انرؼه‪ٛ‬ى انؼان‪ٔ ٙ‬انثذس انؼهً‪ٙ‬‬
‫جــايؼح تـغــذاد‬
‫كــه‪ٛ‬ح انؼــهٕو‬

‫دساعـــح َظــش‪ٚ‬ح ٔػـًه‪ٛ‬ح نجغ‪ًٛ‬ــاخ‬

‫( ‪ )CdSe‬انُـــاَـــٕ‪ٚ‬ح‬

‫اطشٔدح يمذيح إنٗ‬

‫يجهظ كه‪ٛ‬ح انؼهٕو ‪ -‬جايؼح تغذاد‬
‫ْٔ‪ ٙ‬كجضء يٍ يرطهثاخ َ‪ٛ‬م دسجح دكرٕساِ فهغفح‬
‫ف‪ ٙ‬انف‪ٛ‬ض‪ٚ‬اء‬

‫يٍ لثم‬
‫دـغٍ تخ‪ٛ‬د جاعى‬

‫أششاف‬

‫أ‪.‬و‪.‬د‪.‬تششٖ ػثاط دغٍ‬ ‫أ‪.‬د‪.‬يذًذ ذم‪ ٙ‬دغ‪ٍٛ‬‬

‫‪ 2014‬و‬ ‫‪ْ 5341‬‬

‫‪4‬‬
 ‫الخالصة‬
‫ذى ذمغ‪ٛ‬ى ْزا انثذس إنٗ جضئ‪ ٍٛ‬سئ‪ٛ‬غ‪ًْ ٍٛٛ‬ا انُظش٘ ٔانؼًه‪ ، ٙ‬انجضء انُظش٘ انز٘ ذى يٍ خالنّ‬
‫دساعـــح انخٕا ص االنكرشَٔ‪ٛ‬ح انرشك‪ٛ‬ث‪ٛ‬ح نثهٕسج كادي‪ٕٛ‬و‪ -‬ع‪ٛ‬ه‪ُٛ‬ــــ‪ٕٛ‬و راخ انرشك‪ٛ‬ــــــة انًكؼة (‪Zinc-‬‬
‫‪ٔ )blende‬نألتؼاد (‪َ (1.76-2.34‬إَيـــــــــــــــرش تاعرخــــذاو دغاتاخ ي‪ٛ‬كاَ‪ٛ‬ك انكى انرايح ( ‪(AB-‬‬
‫‪ initio‬انًذػٕيح تُظش‪ٚ‬ح كصافح انذاالخ يغ ذمش‪ٚ‬ة االَذذاس انًؼًى (‪ )GGA‬انٗ جاَة طش‪ٚ‬مح خه‪ٛ‬ح‬
‫انٕدذج انكث‪ٛ‬شج نزساخ انهة )‪ٔ (8,16,54,64‬نألتؼاد انصالز ترطث‪ٛ‬ك انششٔط انذذٔد‪ٚ‬ح ٔكزنك دغاب‬
‫عطخ انثهٕسج ( كادي‪ٕٛ‬و‪ -‬ع‪ٛ‬ه‪ُٕٛٛ‬و ) ٔنثؼذ‪ٔ ٍٚ‬ترطث‪ٛ‬ك انششٔط انذذٔد‪ٚ‬ح )‪ (001)-(1x1‬يٍ خالل اضافح‬
‫رسج االٔكغج‪. ٍٛ‬‬

‫ذى دغاب يجًٕع انطالح‪, ،‬فجٕج انطالح‪ٔ ،‬طالحاألسذثاط ‪ٔ،‬األ‪َٕٛٚ‬ح ‪ٔ ،‬ػشع دضيح انركافؤ‪ٔ ،‬ػشع‬
‫دضيح انرٕط‪ٛ‬م‪ٔ،‬أػهٗ دسجاخ االَذالل ‪ٔ.‬كاَد فجٕج انطالح ذرشأح يات‪ (1.73-1.77) ٍٛ‬انكرشٌٔ ‪ -‬فٕند‬
‫تانُغثح نجضء ( انهة) ‪ ،‬ت‪ًُٛ‬ا ف‪ ٙ‬انجضءانخاص تانغطخ فكاَد ل‪ًٛ‬رٓا تذذٔد ( ‪ ) ...0‬انكرٌٕ ‪ -‬فٕند ‪.‬‬
‫ٔلذ ذى انرذم‪ٛ‬ك نُـــٕػ‪ ٍٛ‬يٍ انخـــال‪ٚ‬ا ًْا ) ‪، (8 ,64‬راخ انرشك‪ٛ‬ة انًـــكؼة انثشافــ‪ٛ‬ظ يرؼذدج انخــــال‪ٚ‬ا‬
‫ٔ(‪،(16، 54‬راخ انرشاك‪ٛ‬ة يرٕاص٘ انًغرط‪ٛ‬الخ نخال‪ٚ‬ا يرؼذدج تذائ‪ٛ‬ح(تغ‪ٛ‬طح)‪.‬‬
‫نٕدع َمظاٌ ف‪ ٙ‬طــالح األسذثاط ٔاأل‪ٚ‬ــَٕ‪ٛ‬ح ػُذ ص‪ٚ‬ادج ػذدانزساخ األعاع‪ٛ‬ح )نهة) ػهٗ انؼكظ يٍ رنك‬
‫َالدع اٌ دسجح االَذالل ذضداد يغ ص‪ٚ‬ادجػذدانزساخ األعاع‪ٛ‬ح ( نهة)‪.‬‬
‫ايا كصافح انذاالخ تانُغثح ( انهة)كاَد أػهٗ يًا ػه‪ ّٛ‬ف‪ ٙ‬انغطخ‪ْٔ،‬زا ‪ٚ‬ؼٕد إنٗ ػذو انرًاشم(اَؼذاو‬
‫انرًاشم)تانُغثح نرشك‪ٛ‬ة انثهٕسج ٔػذو األعرًشاس‪ٚ‬ح ف‪ٔ ّٛ‬رنك تغثة ٔجٕد َٕع جذ‪ٚ‬ذ يٍ انزساخ ْ‪( ٙ‬رساخ‬
‫األٔكغج‪.)ٍٛ‬‬
‫ايا ف‪ ٙ‬انجضء انصاَ‪ ٙ‬يٍ انذساعح انؼًه‪ٛ‬ح (انرجش‪ٚ‬ث‪ٛ‬ح ) كاَد يٍ خالل أجشاء انرفاػم انك‪ًٛٛ‬ائ‪ ٙ‬نًادج شاَ‪ٙ‬‬
‫كهٕس‪ٚ‬ذ انكادي‪ٕٛ‬و (‪ )CdCl2‬يغ يادج كثش‪ٚ‬راخ ع‪ٛ‬ه‪ُٕٛٛ‬و ‪ -‬انظٕد‪ٕٚ‬و )‪ٔ (Na2SeSO3‬ترشاك‪ٛ‬ض يخرهفح‬
‫نًادج انغ‪ٛ‬ه‪ُٕٛٛ‬و ‪.‬‬

‫ذى اجشاء انفذض نثهٕسج كادي‪ٕٛ‬و – ع‪ٛ‬ه‪ُٕٛٛ‬و انًذضشج ك‪ًٛٛ‬ائ‪ٛ‬ا ٔرنك يٍ خالل د‪ٕٛ‬د االشؼح انغ‪ُٛٛ‬ح‬
‫ٔكزنك يط‪ٛ‬اف االشؼح انًشئ‪ٛ‬ح – انفٕق انثُفغج‪ٛ‬ح ٔيط‪ٛ‬اف انمٕٖ انزس‪ٚ‬ح ٔل‪ٛ‬اط انخٕاص انكٓشتائ‪ٛ‬ح‬
‫(انرٕط‪ٛ‬ه‪ٛ‬ح انكٓشتائ‪ٛ‬ح ٔذأش‪ٛ‬ش ْٕل)‪.‬‬

‫‪5‬‬
 ‫أظٓش ط‪ٛ‬ف األشؼح انغ‪ُٛٛ‬ح أٌ تهٕسج كادي‪ٕٛ‬و ‪ -‬ع‪ٛ‬ه‪ُٕٛٛ‬و انُإَ‪ٚ‬ح ‪ ) CdSe QDs).‬راخ طــــٕس يكؼة‬
‫)‪ )Zinc- blende‬ػُذ ص‪ٚ‬ادج ذشك‪ٛ‬ض ‪.Se‬‬
‫اشاسخ َرائج ط‪ٛ‬ف انمٕٖ انزس‪ٚ‬ح اٌ ص‪ٚ‬ادج انُغثح انًٕالس‪ٚ‬ح نهغ‪ٛ‬هُ‪ٕٛ‬و انٗ انكادي‪ٕٛ‬و أدٖ انٗ ذمه‪ٛ‬م‬
‫تهٕسج كادي‪ٕٛ‬و ‪ -‬ع‪ٛ‬ه‪ُٕٛٛ‬و انُإَ‪ٚ‬ح ( ‪. )CdSe QDS‬‬ ‫دجى‬

‫أظٓش ط‪ٛ‬ف االيرظاص انفٕق انثُفـــغج‪ -ٙ‬انًشئــ‪ ٙ‬انٗ األصادح انٗ انهٌٕ األصسق يٍ انط‪ٛ‬ف يغ‬
‫ذُالض دجى ‪ QDS‬ػُذ ص‪ٚ‬ادج ذشك‪ٛ‬ض ‪ ْٕٔ Se‬يا ‪ٚ‬شجغ إنٗ ذأش‪ٛ‬شانذـــثظ انكــً‪.ٙ‬‬

‫أظٓشخ َرائج انخٕاص انكٓشتائ‪ٛ‬ح انٗ اٌ تهٕسج ‪ CdSe‬انُإَ٘ نّ طالح ذُش‪ٛ‬ظ تذـذٔد ( ‪) 0.7 – 0.04‬‬
‫انكرشٌٔ فٕند يغ ذغ‪ٛ‬ش دسجاخ انذشاسج ٔاٌ يادج كادي‪ٕٛ‬و – ع‪ٛ‬ه‪ُٕٛٛ‬و شـــثّ يٕطم يٍ َٕع ‪. n‬‬

‫كًا اٌ َرائج لــ‪ٛ‬ى فجٕج انطالح انثظش‪ٚ‬ح ف‪ ٙ‬انجضء انؼًه‪ٔ ٙ‬جذخ آَا ذغأ٘ ( ‪ )1.8‬انكرشٌٔ ‪ -‬فٕند ػُذ‬
‫انُغثح انًٕالس‪ٚ‬ح نم ‪ ْٙ )1:1( Cd:Se‬يرٕافمح يغ انُرائج انُظش‪ٚ‬ح انر‪ٔ ٙ‬جذخ ذغأ٘ ( ‪) 1.77‬‬
‫انكرشٌٔ ‪ -‬فٕند ػُذيا كاَد ػذد رساخ انهة ( ‪ٔ ) 8‬انر‪ ٙ‬ذى دغاتٓا تاعرخذاو طش‪ٚ‬مح َظش‪ٚ‬ح كصافح‬
‫انذاالخ ( ‪ ( DFT‬يمرشَح ترمش‪ٚ‬ثاخ خه‪ٛ‬ح انٕدذج انكث‪ٛ‬شج (‪.)LUC.‬‬

‫‪6‬‬
 Contents

Contents I
Acknowledgment IV
Dedication V
Curriculum vita VI
List of tables VII
List of Figures VIII
List of Symbols and abbreviations XI
Abstract XVIII
Chapter One
Introduction
1-1 Nanocrystal Semiconductor 1
1-2 Properties of II-VI Compounds 2
1-3 Application of II-VI Compounds 4
1-4 The properties and Applications of CdSe 5
Nanocrystals .
1-5 Survey of Experimental and Theoretical for 7
CdSe Nanocrystals
1-6 Aim of the Work 11

Chapter Two
Theoretical Part
2-1 Introduction of Self- Consist Field Method 12
2-2 Schrödinger Equation 12
2-3 Atomic Units 14
2-4 Born – Openheimer Approximation 15
2-5 Hartree Approximation 16
2-6 Hartree – Fock Self- Consistent Field Method 17
2-6-1 Resitricted Hartree- Fock (RHF) Method 20
2-6-2 Unresitricted Hartree- Fock (URF) Method 21
2-7 Linear Combination of Atomic Orbitals 22
(LCAO) And Roothan – Hall Equations.
2-7-1 Slater – Type Orbitals (STOs) 26
2-7-2 Gaussain – Type orbitals (GTOs) 27
2-8 Relativistic Defects 28
2-9 Correlation Corrections to the Hartree- 30
Fock Method.

7
2-10 Ab-Initio Method 31
2-11 Density Functional Theory (DFT) 33
2-11-1 The Hohenberg-kohn (HK) Theorm 34
2-11-2 The Kohn-Sham (KS) Therom 35
2-12 The Density Approximation 36
2-12-1 The Local Density Approximation 36
2-12-2 The Generalized Gradient Approximation 38
2-13 The Large Unit Cell Method 38
2-14 Some Properties of Nanocrystals 45
2-14-1 Total Energy 45
2-14-2 Cohesive Energy 45
2-14-3 Energy Gap 46
2-14-4 Valence Band and Conduction Band Width 47
2-14-5 Dengeracy of energy levels (Density of States) 47
2-14-6 Ionic Charge 47
2-15 Computer Program 48

Chapter Three
Theoretical Results And Discussion

3-1 Introduction 51
3-2 Electronic properties of CdSe 53
3-2-1 Total Energy 53
3-2-2 The geometric structure 55
3-2-3 Lattice constant 57
3-2-4 Cohesive energy 57
3-2-5 Energy gap 59
3-2-6 Valence and conduction bands 60
3-2-7 Ionicity 61
3-2-8 HOMO and LOMO 61
3-2-9 Density of States 62
3-2-10 The comprehensive electronic structure 66
3-3 Oxidization surface part of the CdSeO 68
Chapter Four
Experimental Part
4-1 Introduction 74
4-2 System of Colloidal CdSe Nanoparticles 74
preparation
4-3 Preparation Solutions 75
4-4 X-ray Diffraction 75
4-5 Optical properties 76
4-5-1 Optical Constant 76
8
4-5-2 The Optical Energy Gap Calculation 78
4-6 Absorption Spectrophotometer 78
4-7 Atomic Force Microscope (AFM) 79
4- 8 Intrinsic Mobility 80
Chapter Five
Experimental Results and Discussion
5-1 Introduction 82
5-2 X-ray Diffraction Results of CdSe Nanocrystals 82
5-3 Optical Properties 84
5-3-1 Optical Constant 84
5-3-2 The Optical Energy Gap Calculation 87
5-4 Atomic Force Microscope (AFM) 88
5-5 DC. conductivity and hall effect measurements 92
5-6 Conclusion 94
5-7 Suggestions 95
References 96

9
 Acknowledgement

I would like to express my great thanks to my supervisors prof. Dr.

Mohammed Taki Hussein and Ass.Prof.Dr.Bushra Abbas Hasan for them
supervision and them valuable directions and opinions.
I am also greatly indebted to the Dean of the College of Science, staff of the
physics department in the College of Science, their continuous support and
the optoelectronics Lab. group. And Special thanks for Dr.Thekra K. Abd al
Raheam, and Ph.D. Postgraduate student Omar A. Ebrahim.
My great thanks are expressed to all my friends.

Hasan

11
 Dedication

To : Whom I live and increase my happiness…

my wife , my sons , daughter and my family.

To : All my friends I study with them.

Hasan

11
Curriculum Vita

1 July 1966 ……………...Born Babylon -Iraq

1987 ……………………... B.Sc. Physics/ College of science / University of Basra
2004………………..M.Sc./AL-Rasheed College of Engineering&science/
University of Technology
1988 -2007……………..Iraqi Atomic Energy Organization (LAB.) , The
Ministry of Industry and Minerals (LAB.) , Imam Jafar Sadiq University.
2007-till now…….… College of Imam AL- Kadhim.
2011-2014 ...............Ph.D. Postgraduate student/Physics/University
of Baghdad

List of publications

1- Mohammed T.Hussein ; Bushra A. Hasan ; Thekra K. Abd al Raheam

and Hasan B.Jasim . "(Study the electronic properties of core -
oxidization CdSe nanocrystals.)"; [ IJAIEM, vol.2,Issue 9 ,sep. (2013)]

2- Mohammed T.Hussein ; Thekra K. Abd al Raheam ; Omar A.

Ebrahim , Bushra A.Hasan and Hasan B.Jasim ; "( Study the optical ,
structural and electrical properties of CdSe nanoparticals with
different Se concentrations)"; [ IJEIT, vol.3,Issue 11, May (2014).]

12
 List of Tables

Table Table caption Page

(1-1) The Physical and Chemical properties for CdSe 6
nanocrystals.
(2-1) The most common LUCs that are used for the 42
calculations of band structure of zinc- blende
structure crystals.
(2-2) Some high symmetry points in band structure 42
of solids in units of 2π/a where a is the lattice
constant.
(2-3) Diamond – structured and zinc blende LUCs 44
translational vectors , number of atoms in each
LUC , total number of atoms in nanocrystal
core , and the approximate length of the
corresponding nanocrystal.
(3-1) Electronic structure properties of CdSe 67
nanocrystals for (8 , 16 , 54 , 64 ) core atoms in
LUC.
(3-2) Electronic structure properties of 8 atoms 73
of CdSe- oxidized surface nanocrystals.
(5-1) The different concentrations of CdSe Miller 84
indices , intensity , 2θ , FWHM , interplaner
distance (d), grain size and crystal structure.
(5-2) Optical parameters like absorption coefficient 88
α , extension coefficient ĸʹ , refractive index n ,
real and imaginary dielectric constant ( r ,i
),energy gap Eg , Absorbance A, Transmittance
T, and Reflectance R, at (λ=650nm).

(5-3) Average particles size and Roughness of CdSe 89

with different Se concentrations.

(5-4) Values of  R.T, RH , nH , µ and Type of Conduction 93

for CdSe Thin Film at concentration( (1:1).

13
 List of Figures

Figure Figure caption Page

(1-1) Classification of Nanostructures : I/ Bulk material, 2
II/ Quantum well, III/ Quantum wire, IV/ Quantum
Dot
(1-2) The Energy Gaps of wide gap II-VI Compounds 4
as a function of their Lattice Constants

(1-3) The Structures of CdSe Nanocrystals. 5

(2-1) Orbital Energy-level diagram for Closed-Shell 20

Systems.
(2-2) Orbital Energy-level diagram for Open-Shell Systems 21
.
(2-3) First Brillouin zone of FCC lattice showing symmetry 43
labels.
(2-4) Simplified diagram of the electronic band structure 46
of conductor , semiconductor, and insulator.
(2-5) The flow chart of the computational procedure for 50
obtaining band structure and physical properties of
CdSe nanocrystals.
(3-1) Theoretical and experimental scheme of CdSe 51
nanoparticals.
(3-2) Total energy versus lattice constant of CdSe 54
nanocrystals (8) atoms core in LUC.
(3-3) Total energy versus of lattice constant of CdSe 54
nanocrystals 54 atoms core LUC
(3-4) Total energy as a function of number of core atoms 57
for CdSe nanocrysta
(3-5) Color online CdSe ( 8) atoms core LUC Cubic 56
( Bravais multiple Cell).
(3-6) Color online CdSe (54) atoms core Parallelepiped 56
(primitive multiple cell) LUC.

14
(3-7) Lattice Constant as a function of number of core 57
atoms for CdSe Nanocrystals.

(3-8) The cohesive energy as a function of the number of 58

core atoms for CdSe nanocrystals.

(3-9) The energy gap as a function of number of core atoms 59

of CdSe nanocrystals LUC.
(3-10) Valence band width and Conduction band width as a 60
function of number of core atoms for CdSe
nanocrystals in LUC.
(3-11) The Atomic Ionicity as a function of number of core 61
atoms of CdSe nanocrystals in LUC.
(3-12) HOMO & LUMO as a function of number of core 62
atoms for CdSe nanocrystals.
(3-13) The Density of states as a function of energy levels 63
for CdSe nanocrystals ( 8) atoms core in LUC.
Valence band are shown with bold lines, while
conduction band are shown with ordinary lines. The
energy gap is shown between the two bands (Eg=1.7
7( eV.
(3-14) The Density 0f states as a function of the energy levels 64
for 16 atoms core LUC. Valence band are shown
with bold lines, while conduction band are shown
with ordinary lines. The energy gap is shown
between the two bands (Eg=5.74ev).
(3-15) Density 0f states as a function of the energy levels for 64
54 atoms core LUC. Valence band are shown with
bold lines, while conduction band are shown with
ordinary lines. The energy gap is shown between the
two bands Eg=1.76eV.
The Density 0f states as a function of the energy levels 65
(3-16) for 64 atoms core LUC. Valence band are shown
with bold lines, while conduction band are shown
with blue lines. The energy gapis shown
between the two bands Eg=1.74eV.
(3-17) The density of states as a function of number of core 65
atoms for CdSe nanocrystals.

15
(3-18) Total energy for 8 core atoms oxygenated (001)- 68
(1×1) CdSe surface as a function of lattice constant.

Atomic position of Cd8Se8O4 atoms slab calculations

(3-19) of oxygenated a2 area surface CdSe layers. 70

(3-20) Ionic charge of oxygenated (001)-(1×1) surface slap 71

for 8 atom LUC. as a function of layer depth.

(3-21) Density of states of 8 atoms for surface oxygenated 72

(001)-(1×1) slab having a2 area. Valance band are
shown with blod lines, while conduction band are
shown with ordinary lines. The energy gap is shown
between the two bands which have energy (-2.802 -
-2.775 e.V).
(4-1) The OPTMA SP-3000 UV-Vis. Spectrophotometer 79

(4-2) AFM (Atomic Force Microscope) 79

(4-3) The Experimental Setup to measure the D.C. 81
Conductivity.
(5-1) X-ray diffraction pattern of CdSe nanoparticles at 83
different Se concentrations. a)1:1, b)1:2, c)1:4
(5-2) UV-Visible absorption spectra of CdSe nanoparticles 85
of different Se concentration a)1:1 b)1:2 c)1:4
(5-3) Transmission spectra of CdSe nanoparticles of 86
different Se concentrations a)1:1 b)1:2 c)1:4
(5-4) (h ) 2 versus with hν for CdSe nanoparticles of 87
different Se concentrations a)1:1 b)1:2 c)1:4
(5-5) The AFM images of the surface morphology of the 90
CdSe nanoparticles films of different Se
concentrations a)1:1 b)1:2 c)1:4
(5-6) AFM of CdSe nanoparticles with different Se 91
concentrations in 2D and histogram as a function of
the grain size a)1:1 b)1:2 c)1:4

(5-7) Ln σ versus 1000/T for CdSe thin films at ratio (1:1) . 93

16
 List of Symbols and Abbreviations

1-Alphabetical Symbols

a Lattice constant

B Constant value

a′′,b′′,c′′ Axes

C i The molecular orbital expansion coefficients

c The speed of light

d Distance between two plains

D Grain size

e Electron charge

Ê Eigenvalue of the Hamiltonian

E Energy

En Nuclear Repulsion Energy

Ee Electronic Energy

F Universal Functional of the Density

Fock Hamiltonian matrix element between orbitals 

F 
and 

17
 Ĥ Total Hamiltonian Operator

He Electronic Hamiltonian operator

Hcore Core Hamiltonian

Jij Coulomb repulsion integral


k Wave vector

KB Boltizman constant

Κ Kelvin temperature

ĸʹ Extension coefficient

Kij Exchange potential integral


L Angular momentum

M Nucleus Mass

me Electron Mass

m* Effective Mass

N Nuclei

Nn Radial Normalization Constant

P  Density Matrix

18
p^ Permutation Operator


P Momentum of the particle

R Set of Nuclear Coordinates

R′ Resistance

Rnl Radial Part

r ij Distance Between Particle One and Two

r Radius of Quantum Dot

Ŝ Spin Operator

S The Overlap Integral for Atomic Function   and  

Tˆ Kinetic Energy Operator

T Absolute Temperature

V Volume

Vˆ Potential Energy Operator

W External Potential

Ylm Spherical Harmonics

Z Charge of Nuclei

19
 2- Greek Symbols

 Wavefunction

 Laplacian operator


 Gradient of the Density

 Absorption Coefficient

ʹ Spin up of electron

 Spin Down of Electron

ʹ Full Width at Half Maximum

ΘD Deby Temperature

 High Symmetry point in k space

 Delta Function

 Orbital Energy

 Orbital Exponent

Ɛr Real Dielectric Constant

Ɛ¡ Imaginary Dielectric Constant

   Two-electron integral

21
 i Spatial wavefunction

o Ground state Charge Density

A Total anti symmetric wavefunction

XC Exchange correlation energy

λ Wave length

μ Mobility

μ℮ Mobility of Electrons

μh Mobility of Holes

n, p Concentrations of electrons and holes.

RH Average Hall Coefficient

nH Bulk Concentration

σ Conductivity

α′′,β′′, ɣ Angels

ρ Resistivity

L The Distance Between Two Electrodes

(Aa). Area for Thin Film

Vd Drift Velocity

21
 E Electric Field

nc Complex Refractive Index

n Rear Part

ik Imaginary Part

3- Abbreviations

DFT Density Functional Theory

FCC Face Centered Cubic

GGA Generalized Gradient Approximation

GTO Gaussian Type Orbital

HK Hohenberg-Kohn

HF Hartree - Fock

KS Kohn - Sham

RHF Restricted Hartree-Fock

UHF Unrestricted Hartree-Fock

HOMO Highest Occupied Molecular Orbital

LCAO Linear Combination of Atomic Orbitals

22
LM Lattice Mismatch

LUC Large Unit Cell

LUMO Lowest Unoccupied Molecular Orbital

LDA Local Density Approximation

PBC Periodic Boundary Condition

SCF Self-Consistent Field

STO Slater Type Orbital

LED Light Emitting Diode

LD Laser Diode

QWS Quantum Well

QWRs Quantum Wire

QDs Quantum Dot

LSW Lifshitz- Slyzov - Wagner

TOP Trioctylphosphine

A.U Atomic Unit

a.u Arbitrary Unit

23
 Abstract

This investigation can be classified into two main parts ( theoretical and
experimental). Theoretical investigation is carried out in experimental optical,
structure and electrical study of CdSe nanocrystals. In the first part the
electronic structure properties of II-VI Zinc-blende CdSe nanocrystals for
dimension (1.76-2.34)nm was studied by using Ab-initio Density functional
theory (DFT) at the generalized gradient approximation (GGA) level coupled
with large unit cell (LUC)method of core atoms(8,16,54,64) for 3D periodic
boundary condition (PBC), and in 2D(PBC ) calculations was used to
simulated oxygenated (001)-(1x1) surface. These properties include total
energy , energy gap, cohesive energy , ionicity , valence band width ,
conduction band width , and highest degeneracy of states were calculated.
The energy gap within the range ( 1.73- 1.77 eV ) for core part, while in
surface part is smaller than in core part. Two kinds of cells were investigated
( 8, 64 ) core atoms with a cubic Bravais multiple Cells and ( 16, 54 ) core
atoms with a parallelepiped primitive multiple cells. The cohesive energy and
ionicity are decrease when the number of core atoms increase . The highest
degeneracy of states increases with the number of core atoms increase. The
highest density of state of core part is higher than that at surface part, this is
due to the broken symmetry at the surface discontinuity and existence of new
kind of atoms (oxygen atoms).
In the second part CdSe nanopartical were prepared as a collided by
chemical reaction of sodium selenosulfide (Na2SeSO3) and cadmium chloride
CdCl2 at various concentration of Selenium Se precursor. UV-Visible, X-Ray
Diffraction , Atomic Force Microscope (AFM) and DC.conductivity and Hall
effect are studies of the CdSe QDs.
The X -Ray diffraction pattern shows Zinc-blende phase of CdSe QDs.
24
The results of AFM indicate the increasing the Cd to Se molar ratio cause to
decrease the size of CdSe QDs while increase the roughness .The absorption
spectra show a blue shift with decreasing QDs size which is attributed to
quantum confinement effect.
The D.C conductivity study shows that activation energy is a round (0.04-
0.7)eV with variation temperature and the Hall Effect study indicates that
CdSe is n-type semiconductor.
The experimental results of the energy gap is found (1.8 ) eV for Cd:Se at
ratio (1:1) are compared with theoretical calculation is found (1.77) eV at (8)
core atoms which has been done by using Density functional theory coupled
with large unit cell approximation.

25
Chapter One

Introduction

26
1-1 Nanocrystal semiconductor
In recent years increasing interest has been focused on low
dimensional semiconductor nanostructures(SNCs), particularly quantum dots
and nanowires, due to both their importance in fundamental physics and
their potential for device applications. Quantum dots and nanowires
provide strong confining potentials for both electrons and holes, and thus
exhibit pronounced quantum effects for length scales smaller than the de-
Broglie wavelength.
The phrase semiconductor nanostructures refers to condensed matter
structures typically having dimensions less than Bohr radius of excitons or de-
Broglie wavelength (usually less than 10 nm ), and energy band gaps ranging
above 0 to 4 eV [1].

In general, semiconductor nanostructures can be categorized into three groups

based on their dimensionality. These are known as quantum wells (QWs),
quantum wires (QWRs), and quantum dots (QDs) in decreasing order of their
dimensionality [1] .
The most common semiconductor nanostructures can be classified in terms of
dimensionality. This classification , in fact , is supposed according to the number
of orthogonal directions x, y, z in which the structure patterns have dimensions
Lx , Ly , Lz smaller than , the so-called characteristic length( L0 ) is less than 100
nm [2].

The characteristic length can be defined as the description of the behaviour of

electrons in semiconductors.
Figure (1-1) the density of states change with energy for semiconductor
structures with different geometries. SNCs, belonging to 0-dimensional case, have
discrete energy levels.[3]

27
 Bulk Q. well Q. wire Q. Dot

DOS
s

C.
Eg

V.

I II III IV
LX,LY,LZ > LO LX,LY>L0 > LZ LX >L0 > LY, LZ LO >LX , LY, LZ

Fig. (1-1) Classification of nanostructures : I/ Bulk material,

II/ Quantum well, III/ Quantum wire, IV/ Quantum Dot [3].

1-2 Properties of II-VI Compounds:

Owing to the unique properties of II-VI compounds, including their high
photosensivity to electromagnetic radiation, their almost 100% quantum yield
of radiation recombination and their ability to form solid solutions because of the
last property [4 ]. Also they were attracted technological interest because the
band gap can be tuned and the lattice parameters can be varied [5].
some of the physical and chemical properties of wide-band gap compound
semiconductors were Summarized as follows[6 - 9]:

28
  All II -VI compounds crystallize naturally in a hexagonal or cubic
structure. When the compounds are grown epitaxially, they show zinc
blende structure .
 They are strongly bounded with a nearly equal balance covalent and
ionic bonding.
 High melting points.
 High ionicity.
 High vapor pressures at their melting points.
 High resistivity semiconductors at room temperature.
 High electron affinity and large work function.
 Direct wide band gap energy semiconductors, covers a very large range
extending from (1.48 to 3.6) eV, thus they are promising materials
candidates for many optoelectronic applications in the near IR (1-3
μm) to mid IR (3-5 μm) regions.
 These compounds show high absorption coefficients, and high
efficiency of radiative recombination.
 Many of these systems form a continuous range of solid solutions that
allow the physical properties to be controlled smoothly and the
structural parameters to be optimized by changing their molar
composition.
 The layers of this material system were employed for lattice matching
for a variety of other II -VI compounds. A necessary condition for
fabrication of heterojunction devices.

In both III-V and II-VI compounds the energy gap decreases as we go down
ward in the periodic Table. Thus it is possible to select a semiconductor
compound with a particular energy gap which would determine its
temperature dependent properties.

29
Figure (1-2) the energy gaps of wide gap II-VI compounds as a function of their
lattice constant.

Fig. (1-2) The energy gaps of wide gap II-VI compounds.

as a function of their lattice constants [10].

1-3 Applications of II-VI Compounds:

Wide gap II-VI compounds are expected to be one of the most vital
materials for high –performance opto-electronics devices, especially light emitting
diodes(LEDS), in the short-wavelength region of visible light because of their
direct gap and suitable band gap energies, and laser diodes (LDs) operating
in the blue or ultra–violet spectral range.
Fabrication of short wavelength light emitting diodes has induced increasing
interest in p-type doping II-VI compounds including the tellurium based
compounds (CdSe, CdTe and ZnTe) and alloys (CdHgTe, ZnHgTe and ZnCdTe )
[11]. And ZnSe [ 12].

31
1-4 The Properties and Applications of CdSe Nanocrystals
CdSe is a binary II-VI semiconductor and among this group of
semiconductor compounds it is considered as an important for materials to
development of different optoelectronic devices because of its high photosensitive
nature and suitable intrinsic band gap .The CdSe have two kinds of structure cubic
( Zinc-blend), were the Axes (a′′=b′′=c′′ are equals, angles , α′′ = β′′ = γ are
equals = 90º, and the lattice symbols are P,I ), and hexagonal (wurtzite) were the
Axes (a′′ = b′′ǂ c′′ while the angles are, α′′ = β′′ = 90º, γ = 120º and lattice symbol
is P ), as shown in Fig.(1-3). The study of the properties of ( CdSe ) thin films in
order to improve the performance of devices made of it and also for finding new
applications .

(a) Cubic (Zinc-blende) (b) Hexagonal (Wurtzite)

Fig.(1-3 ) The structures of CdSe Nanocrystals [13]

The II-VI semiconductor nanocrystals , such as CdSe , CdTe , and CdS,

nanocrystals , are the group of nanostructures that have been mostly investigated
because of their high luminescence efficiency and easily adjustable luminescence [
14,15 ], from ultraviolet to near infrared region by nanocrystals size showing the
prospective for optoelectronic devices and biological imaging as well as labeling

31
applications . As a direct wide band gap ( 1.74 eV ) semiconductor, CdSe
nanocrystals may be potentially used in optoelectronics of nonlinear optics and
light emitting diodes .
The nanoparticles are of great scientific interest as they are effectively a bridge
between bulk materials and atomic or molecular structures. Bulk material should
have constant physical properties regardless its size , but at the nano-scale this is
often not the same case . we say begging is size dependent . The properties of
materials change as their size approaches the nano-scale and the percentage of
atoms at in the core becomes significant . Some properties for CdSe as flow in
Table (1-1):

Table (1-1) The Physical and Chemical properties for CdSe nanocrystals.[16].

Molar Appearance Density Refractive Melting point Crystal structure

Mass index
191. 37 1- Black. 5.816 2.5 1268 ºC , 1-wurtzite hexagonal).
g / mol 2-Translucent. g / cm ³ 1541 ºK , 2- Sphalerite (cubic )
3- Adamantine 2314 º F 3- Rock -salt (cubic ).
crystals.
4-Odorless.

The sphalerite CdSe structure is unstable and converts to the wurtzite from upon
moderate heating . The transition start at about ( 403 ºK ) ,and at 973 ºK ) it
completes with in a day. The rock -salt structure is only observed under high
pressure [ 16] .The production of cadmium selenide has been carried out in two
different ways . The preparation of bulk crystalline CdSe is done by the High
Pressure Vertical Bridgman method or High-Pressure Vertical Zone Melting [17] .
Cadmium selenide may also be produce in the form of nanoparticles . Several
methods for the production of CdSe nanoparticles have been developed : arrested
precipitation in solution , synthesis in structure media , high temperature pyrolysis
, sonochemical , and radiolytic methods are just a few [18,19].

32
1-5 Survey of Theoretical and Experimental Study for CdSe Nanocrystal
In 1994, Murray et al.[20]. described a powerful new method " The west coast
method" TBP/TOPO "for synthesizing crystalline, monodisperse, size tunable
CdSe nanocrystals, reported an improvement in the procedure which eliminated the
need for size-selected precipitation, which is a time consuming, wasteful, and
tedious procedure . The principal difference is the temperature of the injection,
which affects the time evolution of the nanocrystal growth as well as the
crystallinity and shape of
the nanocrystals.And second difference is the use of Tributylphosphine (TBP) onto
coordinate to Se instead of the use of (TOP).

In 1997, FROMENT et al.[ 21]. studied the chemical bath deposition of CdSe
layers has been studied by means of quartz crystal microbalance (QCM)
experiments, combined with TEM, HREM observations and EXAFS
measurements. From mass vs time measurements and the modeling of the time
derivative, it is established that the nucleation/growth process occurs via two steps
: the first one corresponds to an instantaneous nucleation of cylindrical nuclei, with
a 2D-growth until a complete coverage of the substrate ; the second one consists of
a 3D-instantaneous nucleation and growth process occurring on sites randomly
distributed on the evolving surface. The addition of silicotungstic acid to the
deposition bath is shown to influence the growth kinetics of the CdSe deposit.
Nanocrystalline deposits with the cubic blend structure are obtained showing
confinement effects. After thermal treatment CdSe shows an hexagonal wurtzite
structure with a large density of defects and the grain size is increased.

In 2006, He Rong et al. [22]. studied Nearly monodisperse CdSe quantum dots
(QDs) have been prepared by a soft solution approach using air-stable reagents in
different organic solvents. This scheme is a supplement to the conventional
thermal decomposition of organo metallic compounds at higher temperatures.

33
CdSe nanocrystals of different sizes could be obtained by simply changing the
solvent. This method is reproducible and simple and thus can be readily scaled up
for industrial production. The reaction process was monitored by the temporal
evolution of the UV-Vis absorption and room temperature photoluminensce
spectra. The structures of the CdSe quantum dots were determined by X-ray
powder diffraction (XRD) and transmission electron microscope (TEM). The
phase transfer of oleic acid–stabilized CdSe nanocrystals into PBS buffer solutions
was also studied for their potentials inbiological applications.
In 2007, Suthan et al.[23] were studied thin films of cadmium selenide (CdSe) as a
semiconductor for optoelectronic applications such as photo detection or solar
energy conversion, due to its optical and electrical properties, as well as its good
chemical and mechanical stability. In order to explore the possibility of using this
in optoelectronics, a preliminary and thorough study of optical and structural
properties of the host material is an important step. Based on the above view, the
structural and optical properties of CdSe films have been studied thoroughly in the
present work. The host material, CdSe film, has been prepared by the physical
vapour deposition method of electron beam evaporation (PVD: EBE) technique
under a pressure of 5 ×10–5 mbar. The structural properties have been studied by
X-ray diffraction (XRD) technique. The hexagonal structure with a preferred
orientation along the (0 0 2) direction of films has been confirmed by the X-ray
diffraction analysis. The films have been analysed for optical band gap and
abserved a direct intrinsic band gap of (1.92 eV). In the same year Rubin et al. [24]
were investigated CdSe thin films which have been grown by chemical bath
deposition (CBD) onto glass substrate with approximately 2000 Å thickness. The
samples were prepared by changing the volume concentration of the solution in the
range of 5-45 ml. of Se, the other growth parameter such as reactive concentration
an stirring remained constant during the growth process. The volume of the
solution of (Se) was varied in order to perform the crystalline phase transformation
from cubic (zinc blende) (ZB) to the hexagonal (wurtzite)(W) structure. The
34
change in the crystalline structure and electrical properties were noticeable,
whereas the growth volume concentration was increased. The characterization of
the samples included optical absorption, X ray diffraction, reflectivity electronic
dispersive spectroscopy and dark electrical conductivity analyses. The optical
absorption spectra allowed to calculate the energy band gap (Eg) value and, hence,
the evolution of (Eg) through the transformation from the cubic crystalline phase to
the hexagonal phase. The X-ray diffraction spectra also showed the complete
microstructural transformation from cubic samples up to the entire hexagonal
lattice for samples with higher volume of the solution of (Se).

In 2010, Kissinger et al.[25] were determined cadmium selenide (CdSe) thin films
on glass substrates were prepared by physical vapour deposition under vacuum
using the electron beam evaporated technique for different substrate temperatures:
room temperature,100, 200, 300± C, respectively. X-ray diffraction analysis
indicates that the films are polycrystalline, having hexagonal (wurtzite) structure
irrespective of their substrate temperature. All the films show most preferred
orientation along (002) plane parallel to the substrates. The microstructural
parameters such as particle size, stress, strain and dislocation density were
calculated. The grain size of deposited CdSe films was small and is within the
range of 18 to 42 nm. The optical absorption spectra of electron beam deposited
CdSe films were studied in the wavelength region of 250–2500 nm. The energy
gap (Eg) values (allowed direct transitions), calculated from the absorption spectra,
ranged between (1.77 and 1.92) eV. The surface morphological quality of electron
beam evaporated CdSe films were analyzed by scanning electron microscope and
atomic force microscope.

In 2011, Dwivedi et al. [26] were studied cadmium selenide nanoparticles grown
on to glass substrate by using chemical bath deposition (CBD) method at room
temperature. The samples are annealed in air for 4h at various temperatures and
characterized by structural, electrical and optical properties. The as-deposited CdSe

35
nanoparticles were in cubic phase with optical band gap (Eg=2.3) eV and,
electrical resistivity of the order of 108 Ωcm. After annealing meta stable
nanoparticles cubic phase transformed into stable polycrystalline hexagonal phase.
Depending upon temperature, decease up to (0.6) eV and 103 Ωcm were observed
in the Eg and electrical resistivity, respectively. These changes have been
attributed to the increase in the grain size of the CdSe nanoparticles. Optical
absorption studies have been recorded. Dependence of optical band gap on
crystallite size has also been studied. In the same year Ouendadji et al.[27] were
determined by based on the self-consistent ab- initio full potential-linearized
augmented plane wave method, the structural, electronic, optical, and
thermodynamic properties of CdSeXTe1-X ternary semiconductor alloys have been
investigated. The exchange–correlation potential was calculated using both the
generalized gradient approximation (GGA) by Perdew–Burke–Ernzerhof (PBE)
and the GGA by Engel–Vosko (EV-GGA). The ground-state properties are
determined for the cubic bulk materials CdSe, CdTe, and their mixed crystals at
various concentrations (x=0.25, 0.5, and 0.75). Deviation of the lattice parameter
from Vegard’s law and the bulk modulus from linear concentration dependence has
been examined. The microscopic origins of the band-gap bowing parameter have
been discussed. Moreover, the refractive index and the optical dielectric constant
for CdSeXTe1-X were studied using different models. Besides, the thermodynamic
stability of the alloys of interest is investigated by means of the miscibility critical
temperature.

In 2012, Hamizi and Johan [28], were studied cadmium selenide quantum dots
(CdSe QDs) synthesized successfully in the absence of trioctylphosphine (TOP)
for 46 minutes and characterized by transmission electron microscope (TEM) and
(XRD) analysis. The TEM image reveals that the( CdSe QDs) were spherical,
compact with a dense structure. The ripening behavior of( CdSe QDs) was
monitored using the red-shift characteristic in the UV-visible absorption peaks, and

36
their size variations were estimated by the quantum confinement theory. The
coarsening effect of CdSe QDs can be observed clearly from (Lifshitz- Slyzov -
Wagner(LSW) plots due to the increase in ripening time and ripening temperature.
The ripening coefficient was obtained to be 6.84 (10 -3) nm3/min. The Arrhenius
plot provides the activation energy value of the ripened samples, which are very
low compared to the sample prior ripening, and was attributed to the domination of
volume diffusion through the liquid phase.

1-6 Aim of the Work

The aim of this work, is to study the electronics structure properties of zinc-
blende structure for Cadmium Selenium Nanocrystals with variable size of core
atoms and surface slab geometry with oxygenated by using Ab- initio density
functional theory coupled with large unit cell approximation, while in experimental
part, the CdSe thin film are prepared by using chemical reaction method, the
optical, structural and electrical properties have been measured.

37
 Chapter Two

Theoretical Part

38
2-1 Introduction of Self - Consistent Field Method
The application of an exact self – consistent field method to a solid is out of the
range of present computers especially when the constituting atoms are of high
atomic numbers so that large number of basis states is needed for the simulation of
the individual atoms . This leads to several approximations that will be described
in this chapter.

2-2 Schrödinger Equation

Schrödinger's space equation is the starting point of most discussions of molecular
structure [29]. The time independent Schrödinger equation is [30].

Hˆ   Eˆ  (2-1)

 is the wave function, called eigenfunction, which describes the spatial motion
of all particles of system moving in the field of force specified by the potential
energy operator V, Ê is the eigen value of the Hamiltonian, Ĥ is the
Hamiltonian operator (gives the kinetic and potential energies of a system of
atomic, nuclei and electrons) [31, 32].

The total Hamiltonian Ĥ , of the system includes electrons and N of the nuclei
may be written in the following form:

             
H ( r , R)  T N ( R)  T e ( r )  V eN ( r , R)  V ee ( r )  V NN ( R) (2-2)

where TˆN ( R), Tˆe (r ) is the kinetic energy operator of nuclei and electrons,
      
respectively, V eN ( r , R) , V ee ( r ) and V NN ( R) as the potential energy operator of
electron – nuclei, electron – electron and nuclei – nuclei respectively, R is the set
of nuclear coordinates and r is the set of electron coordinates .

39
The kinetic energy of the nuclei is expressed as:
  N
1
T N ( R )   
2
(2-3)
A 2M A A
while the kinetic energy of the n electrons is as follows:
  n
1
T e ( r )   
2
i
(2- 4)
i 2me

where MA is nucleus mass, and me is electron mass. The potential energy is

composed of there parts:

   N n
V eN ( r , R)   Z A r Ai
1
(2- 5)
A i

  n
V ee ( r )   rij1 (2- 6)
i j

 N
 ZA ZB R AB
1
V NN  (2- 7)
AB

where ZA , ZB charge of nuclei A and B , rAi distance between nuclei A

and electron i , rij distance between i electron and j , RAB distance between nuclei
A and nuclei B,  i2 is the Laplacian operator for the electron i,  2A is the Laplacian
operator for the nucleus A [33-35] .

2-3 Atomic Units (A.U.)

Hartree's atomic units, Gaussian units, as far as we are concerned , are identical
with the old centimeter gram second (cgs) system of units with the added proviso
that charges are measured in unnamed electronics unit, electrostatic unit ( esu) of
charge . The value of e is thus 4.8032x10-10 esu . Keeping this number at hand is
all that will be required to use Gaussian units in this work. Hartree's atomic units
are obtained by assigning mass , length , and time units so that the mass of the
electron, me = 1, the electron charge, e =1, and  the planck constant,  =1[36].

41
An upshot of this is that the Bohr radius is also 1. If one need to compare
energies that are calculated in that 1 Hartree is 27.211396 (eV) or
me 4
( .u  2
 4.35 x10 18 J  27.211eV ) [37].


2-4 Born-Oppenheimer Approximation

The Born – Oppenheimer approximation is the first major step in simplifying

based on the fact that the nuclear masses are much greater than those of the
electronics. Therefore nuclei move much more slowly, then nearly fixed the
nuclei are compared with the electrons motion [37,38].

In the early days of quantum mechanics, Born and Oppenheimer showed that the
energy and motion of the nuclei and electrons could be separated approximately.
The ratio of nuclear to electron masses is at least 1837/1, thus electrons move
much faster than nuclei. The kinetic energy of nuclei TN can be neglected Since TN
is smaller than Te and VNN is neglected, because VNN is just a constant [34,39].

So equation (2-2) can be reduced to [40].

         
H( r , R )  T e ( r )  V eN ( r , R )  V ee ( r ) (2-8)

The Hamiltonian operator in quantum mechanics became:

   n
1 2 N n n
H( r , R )    
1

i 2
i

A i
ZA r Ai

i j
rij1 (2-9)

41
2-5 Hartree Approximation (Orbital Approximation)
An orbital is a wavefunction describing a single electron. It is necessary to describe
both the spatial and the spin orbital. A spatial orbital  i (r ) is a function of the
position vector r of the electron. An electron can have either spin up or spin down.
The two functions ʹ and  describe the spin of the electron where ʹ
1
corresponds to spin up and  to spin down;  ʹ which belongs to  state and
2
1
 which belongs to  state [41].
2

The orbital approach to approximate solutions of the many-electrons

Schrödinger equation is an attempt to construct a satisfactory approximate of many
electrons wave function from a combination of functions; each is dependent upon
the coordinates of one electron only. For an n electron system, the simplest way to
do this is to associate the n electrons with n one-electron functions  1 , 2 ,...., n
then the total wavefunction (1,2,....., n) as a product of the one-electron function:

(1,2,....., n)   1 (1) 2 (2),...... n (n) (2-10)

Such one-electron function  i is called orbitals and the product function is known
as a Hartree product [37, 41].

The Hartree approximation is useful as an illustrative tool, but it is not a

very accurate approximation. A significant failing of Hartree wave function is that
it dose not reflect the antisymmetric nature of the electrons as required by the Pauli
exclusion principle (a one and only one electron can occupy one energy state) [42-
44].

42
2-6 Hartree-Fock or Self – Consiste Field Method
Quantum mechanics offers the only possible way for the solution of many
problems in physics and chemistry. One of these problems is the calculation of
equilibrium energy or geometry of an atom, molecule or solid. All the theories
applied to such problems are approximations to the Schrödinger equation of many
– particle systems. This Schrödinger equation for two charge particles in atomic
units (where m=e=  =1) is :

N
e2
( Hˆ i  )   (2-11)
i r12

Ze
where Hˆ i  1 / 2 2 i  is called Hartree equation.
ri

 the wave function ,  the energy of the system and r12 the distance
between the two electrons .
To generalize Eq. (2-11) to atoms with several electrons, molecules or solids, the
Pauli exclusion principle should be considered . This principle forbids two
electrons from taken the same spin and space coordinates simultaneously. This
leads to antisymmetrization of the wave function which must be written in the
Slater determinant form:

  [(2ne ) !]  (1) Aˆ[ X1 (1) X 2 (2).........X 2 ne (2ne )]

-1/2 P
(2-12)
P

where  is the permutation operator and X1 (1) is the first basis function of the
first electron that include space and spin degrees of freedom . (2ne) is the number
of electrons of the close shell systems. (-1)p is +1 or -1 for even or odd
permutations respectively. The summation extends over all the possible
permutations (p) of electron coordinates .

43
The first derivation of the many – electrons Schrödinger equations, was due to
Hartree [45,46]. Hartree equations did not take Pauli exclusion principle into
account. Taking this principle into account, Fock [46,47] derived the many –
electrons Schrödinger equations that are generally known as Hartree – Fock
equations or self consist field equations these equations are written in the form
[37].

n
[ H core    (2 J ij  K ij )] i    ij j  (2-13)
i j j

where Jij is called the coulomb integrals,

1
J   ψ* (1)ψ* (2) ψ (1)ψ (2)dτ1dτ 2 ) 2-14)
ij i j r12 i j

and Kij is the exchange integral

* * 1 (2-15)
K   ψ (1)ψ (2) ψ (1)ψ (2)dτ dτ
ij i j j i 1 2
r
12

where Hcore is the one electron Hamiltonian for an electron moving in the field of
bare nuclei, Jij is the direct coulomb repulsion integral due to other electrons
occupying the same orbital  j and Kij is the exchange potential integral that arises
from the anti – symmetry of the total wave function. The doubly occupied wave
function  j is the space part of the original basis states X n(n). The summation
over the index j extends over all the number of basis ne. The left hand side of
equation (2-13) is also known as the Fock Hamiltonian since it reduces Eq. (2-13)
to the standard form

44
 F i    ij j    ne (2-16)
j

In order to solve the ne Hartree –Fock equation (2-16) trial wave functions
 1 , 2 ,..........., ne are used to calculate the Coulomb and exchange potential

integrals and Hcore differential equations. The ne equations (2-16) are solved to
obtain another set of wave functions. The new wave functions are then used to
calculate a new set of potential integrals and Hcore. The cyclic procedure contains
till here no change in the calculated wave functions or potential integrals and H core .
This explains why this method is called self – consistent field method since the
final wave functions produce potential integrals, Hcore and those in turn produce
the same wave functions within a given tolerance when Eqs (2-13) are solved .
The real strength of Hartree-Fock method is applicability to a wide range of
problems. Most of the other methods are restricted to certain kind of calculations.
As an example the Hartree – Fock method has a well – defined procedure for the
calculations of excitations, correlation corrections, relativistic corrections, charge
distribution, mechanical and many other properties . Some of these advantages in
calculations and applications will be made clear in the following sections. There
are two types for Hartree Fock methods:

2-6-1 Restricted Hartree –Fock (RHF) Method

To take the Pauli Principle into account, we must include electron spin in our
wavefunctions. The orbitals that are calculated by the Hartree-Fock method
actually are spin orbitals that are a product of a spatial wavefunction and a spin
function [48].
i  i , spatial( x, y, z) ori  i , spatial( x, y, z) ( 2-17)

45
In spin orbital , i ,spatial( x, y, z) is the spatial wave function describing the probability
of finding the electron in space and  ʹ or β are spin wave functions .
For a closed shell system, in which all of the electrons are paired, during the
solution of the self-consistent field equations, one can restrict the solution so that
the spatial wave functions for paired electrons are the same. This is called a
restricted Hartree-Fock calculation (RHF) and generally is used for systems in
which all the electrons are paired . This is described in figure (2-1) .

Fig. (2-1): Orbital energy – level diagram for closed – shell systems [41]

2-6-2 Unrestricted Hartree-Fock (UHF) Method

For open shell systems that contain unpaired electrons, the assumption made in the
restricted Hartree-Fock method won't work. There is more than one way of
handling this type of problem [48].
One way is not to constrain pairs of electrons to occupy the same spatial orbital, is
called unrestricted Hartree-Fock method (UHF). In this method there are two sets
of spatial orbitals – one with spin up (α′ ) electrons and other spin down (β)
electrons. This leads to two sets of orbitals as shown in Fig.(2-2) .

46
 E

α′ β

Fig.(2-2) : Orbital energy – level diagram for open – shell systems [41].

2-7 Linear Combination of Atomic Orbitals (LCAO)

and the Roothaan – Hall equations
From the preceding sections, Hartree-Fock equations are integrodiffrential
equations and their solution is difficult since integral and differential equations are
time consuming even for main – frame computers. An approximate method resides
on finding the appropriate combination of a given number of basis states can be
used. This is performed by the variation of the combination coefficients to obtain
the lowest possible total energy of the system [37]. This method is called linear
combination of atomic orbitals (LCAO). It also referred to as the tight binding
approximation. As suggested by its name the basis states are the wave functions of
the atoms that form the molecule or the solid:

N
 i   C i  (2-18)


47
where C i is the combination coefficients and N is the number of combined
atomic orbitals.
This method has several advantage and some disadvantages. Its main advantages
are:
1- The great reduction in computational efforts and time needed to perform
these calculations since integrodiffrential equations are avoided and replaced
by linear algebraic equations. The basis set expansion is fixed and all
integrals and differential equations are only needed to be solved once. The
further iterations only change the coefficients of the linear combination of
these integrals or differential equations.

2- The inter pretability of the final eigenvectors in terms of the constituting

atomic orbitals is possible, and a better understanding of these final states is
gained.

3- The integro differential equations are numerically solved giving rise to

errors that are accumulated when performing further iterations. On the other
hand, the evaluation of integrals and differential equations in terms of
atomic orbitals can be completely analytical. The intgrodifferential
equations can only be solved in high precision calculations whereas, the
algebraic equations can be solved in low precision .

The main disadvantage is that the combined wave functions might not be perfectly
suitable for the description of the final Hartree-Fock states. This proved not to be
the case in most of the calculations and can be easily overcomed by the use of
large number of wave functions to be combined to form the final Hartree-Fock
states.
As mentioned above, the molecular or solid wave functions are constructed in
terms of the constituting atomic orbitals. The determination of the expansion
48
coefficients is based on the variational methods in quantum mechanics. After
selecting the basis states, the coefficients C i may be adjusted to minimize the
expectation value of the orbital energy  . The variation of these coefficients
leads to a set of N algebraic equations that are called Roothan – Hall equations
[49].


( F   S   )C i  0  1,2...........N (2-19)

where F  is Fock matrix

 is orbital energy
S   is overlap of atomic function   and 

C i is molecular orbital expansion coefficient

The summation over the index  extends over the number of orbitals N .

The normalization of the wave functions leads to the following equations


 
C S  C*
i Vi 1 (2-20)

In the above equations S v is the overlaped integral defined by:

S      *  dV (2-21)

where the integration is over all space and dV is an infinitesimal volume element
in three – dimensional space. F  in Eq.(2-19) is the Fock operator matrix
element defined by:

F   H     P [    1 / 2   ]
core
(2-22)
 

49
 core
where H  is the matrix element of the Hamiltonian of a single electron in
the field of the nuclei . Its operator representation is:

     (1) H
H core  (1)dV1
* core
(2-23)

ZA
and H core  1 / 2 2  
A r

where ZA is the charge of nucleus A and the summations is over all nuclei . The
quantities between parentheses in eq.(2-22) is called the two – electron integrals
differential overlap matrix elements defined by the following equation:

1
      * (1) (1)( )  (2) (2)dV1dV2
*
(2-24)
r12

At this stage there are no approximations. However, one can utilize the fact that
many of the integrals are very small or zero and begin to neglect systematically
some of the matrix elements.

In equation (2-22) the two – electron integrals are multiplied by the density matrix
Pv which is defined by:

Occ
P   2 C i Ci
*
(2-25)
i

The summation is over occupied orbitals only. The factor of two in equation (2-
25) indicates that there are two electrons in each orbital for closed shell systems .
The density matrix is the most precious output of the above calculations since by
using it all the physical properties of the solid can be determined .

51
The total electronic energy is given by :
E e  1 / 2 P ( F   H  
core
) (2-26)
 

This energy is added to the inter – nuclear potential energy is:

Z AZ B
En    (2-27)
A B  A R AB

To give the total energy:

ET  E n  E e (2-28)

There are two types of the function representation of minimal basis sets of the
atomic orbitals mostly used that are either of Slater type or of Cartesian Gaussian
type. The different types of orbitals differ by the form of the radial function Rnl (r )
[50,51].

2-7-1 Slater-Type Orbitals (STOs)

The slater – type function is defiend as :

 nlm
STO
(r , ,  )  Rnl (r )Ylm ( , ) (2-29)

where n, l and m are the principle , angular momentum and magnetic quantum
numbers, respectively, Ylm ( ,  ) is a spherical harmonics and Rnl (r ) is the radial part
of the atomic functions Rnl (r ) for (STOs) is [52,53].

R (r)  N n r n 1exp( ζr)

nl
and (2-30)
Ylm ( ,  )   l ( )m ( )

51
where Nn is the radial normalization constant,

(2 ζ ) n 1/2
Nn  (2-31)
[(2n)!]1/2

and  is the orbital exponent, these functions arise from a potential.

2-7-2 Gaussian-Type Orbitals (GTOs)

The Gaussian orbitals are largely used today in atomic and molecular
computations. The greatest advantageous type of these functions is the easily
integral polycentric functions. They are less satisfactory than STO as
representations of atomic orbitals because they do not have a cusp at the origin.
The general form of (GTOs) is the same for (STOs), but the difference is in the
exponents [53-55].

nlm (r ,  ,  )  Rnl (r )Ylm ( , )

 GTO

where Rnl (r )  N n r n1 exp( r 2 ) (2-32)

N n  2 n1[(2n  1)!!1 / 2 (2 ) 1 / 4  ( 2n1) / 4 ] (2-33)

In Gaussian type orbital (GTOs), the radial type depends on exp (r 2 ) rather than
exp (r ) . This makes the solution of the electron – electron repulsion integrals
analytically possible, where as with STOs they can only be solved numerically.
The advantage in Gaussian type orbitals is the central four – electron integrals
which appear in self - consistent field may be reduced to central two – electron
integrals [56-58] .

52
2-8 Relativistic effects
Relativistic effects are taken spin-orbit interactions for same or different electrons
into account .
Relativistic effects are important in atomic physics for high atomic number (Z)
nuclei. They have the same parallel effects in solid state and molecular physics.
Relativistic effects can be neglected for crystals containing atoms like carbon
(Z=6) or silicon (Z=14), but their effects on electronic band structure cannot be
neglected for atoms like germanium (Z=32), tin (Z=50) or lead (Z=82)
The incorporation of relativistic effects can be done in two different ways, the first
is by the solution of Dirac relativistic equation and the second is by the use of
perturbation theory. The first method is being more accurate and complicated, the
second being easier and simpler with their results easier to interpret [46].

1- relativistic correction (H1) to the kinetic energy:

P4
H1   (2-34)
8m 3 c 2

where p and m are the momentum and mass of the particle, c the speed of
light. This term has a negative expectation value and its effect on s states (l=0) is
more pronounced than the other states of higher value of the angular momentum (
l ).

2- Spin – orbit term (H2):

1 dVP
H2  2 2
L.S (2-35)
2rm c dr

53
where VP is the potential, L is angular momentum operator and S is the spin
operator. This term has the effect of splitting levels of l≠0 and it has no effect on s
states (l=0).

3- Relativistic correction to the potential energy (Darwin correction) (H3):

h2
H3   2VP (2-36)
32 2 m 2 c 2

This term has a positive expectation value and affects s states only .

From the presentation, the first and third terms affect mainly the S states with
different directions and do not produce any splitting. The second term is the only
term that produces further splitting to the energy levels. The splitting in atoms
depends on the total angular momentum j that is given by:

j  l  1 / 2 for l  0

(2-37)
j  1 / 2 for l  0,

So that the total relativistic effect on the p1/2 is the same as for the S1/2 in
atoms.
Since splitting of the p states is due to the spin – orbit correction only , the only
relativistic correction that can be measured directly in experiment is the term (H3).

2-9 Correlation Corrections to the Hartree-Fock method

The main deficiency of Hartree-Fock theory is the lack of correlation between
motions of electrons. Correlation energy is defined as the difference between the
Hartree – Fock and exact (non relativistic) energy [59].

E(Correlation)=E(exact)-E(Hartree-Fock) (2-38)

54
The correlation correction to the initial error inhibited in Hartree –Fock
calculations is due to the fact that only one single determinant is included in
Hartree-Fock calculation. One obvious example of correlation correction
importance is the F2 molecule. This molecule is predicted to unstable in the exact
Hartree-Fock calculations[59,60]. However adding correlation corrections to the
Hartree-Fock calculations will result in nearly exact experimental bond
dissociation energy. This deficiency is also obvious when we try to describe the
dissociation of a hydrogen molecule to two separate hydrogen atoms [59]. The
associated hydrogen molecular wave function in Hartree-Fock calculations is
contaminated with incorrect compounds that attach the two electrons to one atom.
In order to correct this error several determinants should be included in the
calculations. This method is called configuration interaction (CI) which relies on
the variation of the energy of multiple – determinant wave functions to obtain the
lowest possible energy of the system. The simplest CI calculations that can be
performed include the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO). These calculations are frequently called
HOMO-LUMO calculations[ 61].
Since the hydrogen molecule has only two basis, a full configuration interaction
can be performed with the HOMO-LUMO type calculations . In order to peform
these calculations, the two – electron repulsion integrals and core Hamiltonian
integrals should be transformed in terms of the final Hartree-Fock molecular
orbitals [62].
In order to calculate the CI corrections can use McWeeny rules for this purpose
[62]. Other methods of correlation are available and are widely used to correct the
calculated Hartree-Fock total energy . One of these methods that can be applied to
molecular and solid calculations is the Moller-Plesset perturbation method [63,64].

55
2-10 Ab-initio Method
Ab –initio is the Latin term for "from first principles", or "from scratch this name
is given to computations which are derived directly from theoretical principles ,
with no inclusion of experimental data. Most of the time is referring to an
approximate quantum mechanical calculations. The approximations made are
usually mathematical approximations, such as using a simpler functional form for a
function or getting an approximate solution to the differential equation [65] .
The most common type of Ab-initio calculation is called a Hartree – Fock
calculation (HF), in which the primary approximation. This means that columbic
electron – electron repulsion is not specifically taken into account. However, its
net effect is included in the calculation. This is a variational calculation, meaning
that the approximate energies calculate are all equal to or greater than the exact
energy. The energies calculated are usually in units called Hartree. Because of the
central field approximation, the energies from HF calculations are always greater
than exact energy and tend to a limiting value called the Hartree-Fock limit. The
second approximation in HF calculations is that the wavefunction must be
described by some functional form, which is only exact for a few one electron
systems. The functions used most often are linear combinations of Slater type
orbitals (exp (r ) )or Gaussian type orbitals (exp (r 2 ) ), the wave function is
formed from linear combinations of atomic orbitals or more often from linear
combinations of basis function. Because of this approximatation, most HF
calculations give a computed energy greater than the Hartree-Fock limit [66] .
In Ab-initio methods, 100% of the model is done mathematically, based
primarily on Schrodinger's Equation. Using several constants, such as the speed of
light, Planck's constant, and the masses of the electrons and nuclei. Ab-initio
methods can be used to calculate a wide variety of properties [53]. The majority of
the currently available software packages have the ability to perform Ab-initio
calculations. Ab-initio does not mean that Schrödinger equation is solved exactly.

56
It means that a method is selected to give a reasonable approximation to the
solution of Schrödinger equation and the selecting of a basis set that will
implement a method in reasonable way [67] The primary advantage of Ab-initio
methods is the accuracy with which calculations are performed. Ab-initio is the
most accurate and precise of all of the currently available methods in molecular
modeling. Ab-initio methods can currently only be applied to small systems. As
computing power improves (primary through the use of massively parallel
supercomputer), an exact solution of the Schrödinger equation is applicable [58] .
Also, there are large number of parameters which are used in the system of
computers programs to do the calculations necessary for the solution of
Schrödinger equation. These calculations involve an enormous number of difficult
integrals for large systems. Ab-initio computational methods solve all of these
integrals without approximation. Ab –initio methods are the most reliable for small
and medium-sized systems, but are prohibitively time – consuming for large
systems [68].
For large systems, semiempirical methods have been developed which ignore or
approximate some of the integrals used in Ab-initio methods. To compensate for
neglecting the integrals, the semiempirical methods introduce parameters based on
molecular data. Commercial software packages are available for both Ab-initio and
semiempirical calculations [69].

2-11 Density Functional Theory (DFT)

DFT is a quantum mechanical modeling method used in physics and
chemistry to investigate the electronic structure (principally the ground state) of
many-body systems, in particular atoms, molecules, and the condensed phases.
With this theory, the properties of many-electrons system can be determined by
using functionals, which in this case is the spatially dependent electron density.
Hence the name density functional theory comes from the use of functionals of the

57
electron density. DFT is among the most popular and versatile methods available
in condensed-matter physics, computational physics, and computational
chemistry[70].

Density functional theory is an extremely successful approach for the description

of ground state properties of metals, semiconductors, and insulators. The success
of density functional theory (DFT) not only encompasses standard bulk materials
but also complex materials such as proteins and carbon nanotubes, While DFT in
principle gives a good description of ground state properties, practical applications
of DFT are based on approximations for the so-called exchange-correlation
potential which gives superior accuracy to Hartree-Fock theory (Ab-initio and
semiemperical approximations). The exchange-correlation potential describes the
effects of the Pauli principle and the Coulomb potential beyond a pure electrostatic
interaction of the electrons. Possessing the exact exchange-correlation potential
means that the many-body problem is solved exactly, which is clearly not feasible
in solids[71] .

2-11-1 The Hohenberg-Kohn theorem (HK)

The formal bases of DFT are the theorems formulated in 1964 by Hohenberg and
Kohn [72]. DFT was put on a firm theoretical footing by the two Hohenberg–Kohn
theorems (HK). The original HK theorems held only for non-degenerate ground
states in the absence of a magnetic field, although they have since been generalized
to encompass these [73].

1st HK Theorem: The first HK theorem demonstrates that the ground state
properties of a many-electrons system are uniquely determined by an electron
density that depends on only 3 spatial coordinates. It lays the groundwork for
reducing the many-body problem of N electrons with 3N spatial coordinates to 3
spatial coordinates, through the use of functionals of the electron density. This

58
theorem can be extended to the time-dependent domain to develop time-dependent
density functional theory (TDDFT), which can be used to describe excited states
[74].

2nd HK Theorem: The second HK theorem defines an energy functional for the
system and proves that the correct ground state electron density minimizes this
energy functional [75].

The energy functional of the density E [ρ] is:

E[  ]  F[  ]   w(r )  (r )dr (2-48)

where F is a universal functional of the density. Once the external potential w(r)
has been fixed, the energy functional E [ρ] has its minimum, the ground state
energy E0, at the physical ground state density ρ0 (r):

EO  E[  O ] (2-49)

The Hohenberg-Kohn (HK) theorems have the limited purpose to prove that a
universal functional of the electron density exists, they do not derive its actual
expression. A direct minimization of the functional (2-48) is usually not
applicable, because no good expression for the kinetic energy as a functional of ρ
is known, except for simple metals. The Kohn-Sham (KS) scheme, a reformulation
of the theory based on the KS orbitals instead of the mere density, is the starting-
point of most of the actual calculations.

59
2-11-2 The Kohn-Sham Scheme
The density functional theory (DFT), in the Kohn-Sham formalism, provides a
powerful computational scheme, which allows to determine exactly the ground-
state properties even of complex systems of interacting particles, simply solving a
single particle- like equation.

Kohn-Sham density theory [76] is widely used for self consistent field electronic
structure calculations of the ground state properties of atoms, molecules, and
solids.

The Kohn and Sham equation is :

 1 
eff
hKS i    ri 2  w(r )i i i (2-50)
 2 

where w(r ) is the external potential ,  i is the eigen function

Within the framework of Kohn–Sham DFT (KS DFT), the intractable many-body
problem of interacting electrons in a static external potential is reduced to a
tractable problem of non-interacting electrons moving in an effective potential. The
effective potential includes the external potential and the effects of the Coulomb
interactions between the electrons, e.g., the exchange and correlation interactions.
Modeling the latter two interactions becomes the difficulty within KS DFT. [77].

2-12 Density Approximations

The classes of approximations to the exchange-correlation energy functional in
density functional theory that depend solely upon the value of the electronic
density at each point in space are divided to:

61
2-12-1 The Local Density Approximation
A common approximation is the so-called local density approximation (LDA)
which locally substitutes the exchange-correlation energy density of an
inhomogeneous system by that of an electron gas evaluated at the local density.
While many ground state properties (lattice constants, bulk moduli, etc.) are well
described in the LDA, the dielectric constant is overestimated by 10-40% in LDA
compared to experiment [78].
The Local Density Approximation (LDA) consists of expressing the functional
dependence of the exchange-correlation energy on the density with a simple
dependence on the local value of the density. Since the LDA is exact in case of
homogeneous systems, it has been thought to be suitable to describe those physical
systems where the charge density varies slowly, like metals [79].
The major problem with DFT is that the exact functionals for exchange and
correlation are not known except for the free electron gas. However,
approximations exist which permit the calculation of certain physical quantities
quite accurately. In physics the most widely used approximation is the local-
density approximation (LDA), where the functional depends only on the density at
the coordinate where the functional is evaluated:


LDA
E XC [n]   XC (n)n(r )d 3 r (2-51)

The local spin-density approximation (LSDA) is a straight forward generalization

of the LDA to include electron spin: [80--82].


LSDA
E XC [n , n ]   XC (n , n )n(r )d 3 r (2-52)

Highly accurate formulae for the exchange-correlation energy density

have been constructed from quantum Monte Carlo simulations of jellium. In this

61
theory, only exchange – correlation energy E XC  E X  EC as a functional of the
electron spin densities n (r )and n (r ) must be approximated.

2-12-2 The Generalized Gradient Approximation

The generalized gradient approximation (GGA) are still local but also take into
account the gradient of the density at the same coordinate:[83,84].

  
GGA
E XC [n , n ]   XC (n , n , n , n )n(r )d 3 r (2-53)

Where n  n  n ,Using the latter (GGA) very good results for molecular
geometries and ground-state energies have been achieved. In comparison with
LSD, GGA's tend to improve total energy, atomization energies, energy barriers
and structural energy differences.

2-13 The Large Unit cell method

In order to perform cluster calculations to simulate the bulk of a solid, the cluster is
chosen such that its surface has the minimum possible area to reduce the number of
dangling bonds or the number of saturating atoms. This restricts the number of
atoms to certain numbers since all the n – neighbors of the central atom have to be
added to the calculations. In addition the large unit cell (LUC) gives us the profits
gained from cyclic boundary in simulating the solid. The LUC alters the shape and
the size of the primitive unit cell so that the symmetry points in the original

Brillouin zone at a wave vector ( k ) become equivalent to the central symmetry
point in the new reduced zone [85] .
In the LUC method, a unit cell of a multiple of either the Bravais or primitive cell
of the zinc blende structure is used to represent the bulk of the crystal . Some of
these LUC are given in terms of the 8 atom Bravais unit cell or 2 atom primitive
cells. Cells that have integral multiple of lattice constant (a) are multiples of

62
Bravias cell (8 , 64 atoms), while the others multiples of primitive cell (16 , 54 and
128 atoms).

It should be pointed out that the number of atoms in LUC is not the number of
atoms in the nanocrystals; It is only the number of atoms in the core of the
nanocrystal that nearly have prefect zinc blende structure. These atoms are at least
one lattice constant distant from the surface. As a result all the bonds between
atoms have exactly the same value. The primitive unit cell can be represented by
the following matrix [86]

1 1 0
 
1 / 2a 1 0 1  (2-39)
0 1 1
 

where a is the lattice constant of the Bravais lattice.

In order to choose a LUC, one must multiply the above matrix by a convenient
transforming matrix that will result in a new cell with different shape or size. To
transform the primitive cell to the Bravais lattice cell the following matrix can be
used: [87].

 1 1  1
 
 1 1 1  (2-40)
1 1 1 
 

This will result in the following matrix:

 2 0 0
 
1 / 2a 0 2 0  (2-41)
 0 0 2
 

63
As can be seen from this matrix, the Bravais lattice is four times the volume of the
primitive unit cell and has a different shape from the original primitive cell . The
bravais lattice will be used as the LUC in this work.

Another feature of the LUC is the applicability of the k =0 approximation. the first
Brillioun zone of a given lattice with a lattice constant in the one dimensional case
is defined by the wave vector


  / a  k   / a (2-42)

However this zone will become smaller when choosing a LUC lattice with a lattice
constant 2a and is defined by the wave vector


  / 2a  k   / 2a (2-43)

As can be seen from the above argument that choosing a LUC lattice with a lattice
constant large enough will make all points in the first Brillouin zone close to the

point k = 0 in the three-dimensional case . As a consequence the self – consistent
equations should be solved only for the points at the origin of the first Brillouin

zone . This approximation is called the k =0 approximation and is used frequently
in solid state physics whenever such large cells are encountered [88]. The use of

the k =0 approximation will result in a great simplifications of the self – consistent
field equations .
In LUC method only lattice constant is optimized for the core part. However, the
surface part bond lengths and angles still need to be optimized because of the
surface reconstruction.

64
 The basic idea of LUC is computing the electronic structure of the unit cell

extended in a special manner at k = 0 in the reduced Brillion zone. This equivalent
to a band structure calculation at those k-point which transform to Brillion zone
center on extending the unit cell.
Calculations on LUCs are centered and limited number of atoms per LUC as
described in Table (2-1). The most common LUCs that are used for the
calculations of band structure of zincblende structure crystals is listed with the
high symmetry points that are obtained from the solution of Hartree – Fock
equations for these crystals [89] .

65
Table (2-1): The most common LUCs that are used for the
calculations of band structure of zinc blende structure crystals [90].
Number of atoms in the LUC High symmetry points
8  ,3X

16  ,3X,4L

54  ,3X,4L, 6

64  ,3X,4L, 6 ,6W,12 

128  ,3X,4L, 6 ,6W,12  and 32 inner

points of reduced Brillion zone

Where the high symmetry points related with coordinate k space as show in the
table (2-2) and shown in Fig. (2-3) :

Table (2-2) : Some high symmetry points in band structure of solids

in units of π/2a where a is the lattice constant [90] .

High symmetry points Coordinates k space π/2a

 (0 , 0 , 0)
X (1 , 0 , 0)
L (1/2 , 1/2 , 1/2)
K (3/4 , 3/4 , 0)
Δ (1/2 , 0 , 0)
W (1 , 1/2 , 0)
 (1/2 , 1/2 , 0)

66
 Fig.(2-3): First Brillouin zone of (FCC) lattice showing symmetry
labels[91].
Some of these LUCs are given in Table (2-3), Diamond – structured and zinc
blende LUCs translational vectors, number of atoms in each LUC , total number of
atoms in nanocrystals core, and the length of the nanocrystals for the multiples of
Bravais cell (8, 64, 216 atoms), while the others (16,54,128, 250 atoms) are
multiples of primitive cell. The two atom primitive cell is unacceptable central cell
for LUC calculations since the interaction range (one Bravais lattice cell constant)
is greater than the dimensions of the primitive cell [87].

67
Table (2-3) : Diamond–structured and zinc blende LUCs
translational vectors , number of atoms in each LUC , total number
of atoms in nanocrystal core , and the approximate length of the
corresponding nanocrystal [92] .

Number Total Length of

Translation vectors of atoms number nanocrystal
in LUC of atoms
a(1/2,1/2,0),a(1/2,0,1/2),a(0,1/2,1/2) 2 - -
a(1,0,0),a(0,1,0),a(0,0,1) 8 216 3a
2a(1/2,1/2,0),2a(1/2,0,1/2),2a(0,1/2,1/2) 16 325 3.44a
3a(1/2,1/2,0),3a(1/2,0,1/2),3a(0,1/2,1/2) 54 470 3.89a
2a(1,0,0),2a(0,1,0),2a(0,0,1) 64 512 4a
4a(1/2,1/2,0),4a(1/2,0,1/2),4a(0,1/2,1/2) 128 738 4.52a
3a(1,0,0),3a(0,1,0),3a(0,0,1) 216 1000 5a
6a(1/2,1/2,0),6a(1/2,0,1/2),6a(0,1/2,1/2) 250 1092 5.15a

68
2-14 Some Properties of Nanocrystals
2-14-1 Total Energy
The total energy of a molecular system is the sum of the total electronic energy,
and the energy of internuclear repulsion. The geometry optimization is the process
through which the equilibrium positions of atomic nuclei are specified , within a
given symmetry restriction . In most of the cases the geometry optimization is
necessary since the exact position of the atoms, which enter parametrically the
electronic Hamilitonian are not known exactly. Thus, geometry optimizations,
which involve the calculation of forces in addition to the calculation of energies are
an essential ingredient of most of the calculations [93,94,] .

2-14-2 Cohesive Energy

The cohesive energy of a solid is defined as the energy required for transforming
the crystals into isolated free atoms. The calculation of the cohesive energy
requires a value of the total energy for the solid and for the free atoms [95] The
cohesive energy is calculated from the total energy of LUC .
If the LUC is composed of n atoms the cohesive energy is given by [96] :

Ecoh  Etotal / n  E free  Eo (2-44)

where: Ecoh is the total cohesive energy per unit cell
Efree is the free atoms energy
Eo is the vibrational energy of the ground state
n number of core atoms in LUC (8,16,54,64)

69
2-14-3 Energy Gap
In solid state physics, a band gap, also called an energy gap, is an energy range in a
solid where no electron states exist. In a graph of the electronic band structure of a
solid the band gap generally refers to the energy difference (in electron volts)
between the top of the valence band, which is called the highest occupied
molecular orbital (HOMO), and the bottom of the conduction band, which is
called the lowest unoccupied molecular orbital (LUMO), found in insulators and
semiconductors [97] and this shown in Fig.(2-4).

Conductor

Fig.(2-4): Simplified diagram of the electronic band structure of

conductor, semiconductor, and insulator [97].

It is the amount of energy required to free an outer shell electron from its orbit
about the nucleus to become of mobile charge carrier, able to move freely within
the solid material . In conductors, the two bands often overlap , so they may not
have an energy gap [98].

2-14-4 Valence Band and Conduction Band Width

The valence band is lower in energy than the conduction band and is generally
completely full in semiconductors, at absolute temperature (T=0 oK). When solid is
heated or disturbed , electrons from the valence band jump out of the band across

71
the band gap and into the conduction band , making the material conductive . The
Fermi level separates the valence band from the conduction band . In metals the
valence band overlap with the conduction band [99] .

2-14-5- Degeneracy of Energy levels ( Density of States )

The density of states (DOS) of a system describes the number of states per interval
of energy at each energy level that are available to be occupied by electrons [100] .
In physics two or more different physical states are said to be degenerated if they
are with the same energy level . Physical states differ if and only if they are
linearly independent. An energy level is said to be degenerated if it contains two or
more different states. The number of different states at a particular energy level is
called the level's degeneracy [101].
2-14-6 Ionic Charge

The whole nanocrystals in our model are represented by a heterojunction ( a

junction formed between two dissimilar semiconductors, a good combination for
heterojunction of two materials with similar lattice constants and different energy
gap) [101]. The heterojunction (oxygen atom) of the surface and CdSe core, which
the surface represents the outer most four layers and the core by the rest of the
internal region of nanocrystal. The matching of the two regions at the junction
results in a band bending because of the electric fields and different charges at the
two sides of the junction [102].

71
2-15 Computer program

Gaussian 03 is generally referred to as an Ab-initio electronic structure program

and 03 referred to year 2003. Gaussian, a commercial quantum chemical software
package from Gaussian , Incorporation is considered by many to be the industry
standard in the area of molecular modeling and computational chemistry .
Gaussian is capable of running all of the major methods in molecular modeling ,
including molecular mechanics; Ab-initio ; semi – empirical , and density
functional theory (DFT) . It is probably best known for its robustness in running
Ab-initio and DFT calculations . The name Gaussian comes from the use of the
Gaussian type Orbitals that Gaussian's originator, John Pople, used to try to
overcome the computational difficulties that acrose from the use of Slater Type
Orbitals. Most readers will know the Gaussian mathematics by two other names –
a normal distribution , or perhaps as a bell – shaped curve. A number of
researchers , such as S.F.Boys and Isaiah Shavitt , Pople , quite brillitly ,
recognized that the (relatively) simple substitution of a series of Gaussian functions
for the Slater function would greatly simplify the rest of the calculation of the
Schrödinger equation [103]. Pople's work resulted in the standard use of these
Gaussian functions. Virtually every other developer of Ab-initio computional
chemistry software uses this technique. Pople , by the way , was awarded in the
1998 Nobel Prize in Chemisty (along with Walter Kohn) [104] . The program of
Gaussian needed some requirement to operate [105] :

The individual program of Gaussian step serves to perform a specific task as in the
following:

1. Specification of the positions of atoms and the kind of states that are given as
an input data.

72
2. The (overlap, core Hamiltonian and two electron) integrals are calculated and
stored.

3. The Fock matrix F is calculated from an initial guess of the wavefunction with

the calculated integrals in the previous step.

4. Calculation of the density matrix from the new eigenvalue.

5. Calculation of the total electronic energy from the density matrix.

6. Calculation of a new Fock matrix from the new eigenvalue.

7. Steps 4 and 5 are repeated until self-consistency is achieved.

8. The total energy compared with the previous one and when the total energy
differs from the preceding one, steps 4,5 and 6 are repeated with gradually
improving molecular orbitals (MOS), until the electronic energy converges.

9. Correlation correction (DFT) are added.

10.Calculation of the electronic structure of CdSe .

Fig.(2-5) the flow chart of the computational procedure that is used in the present
calculations.

73
 Start

Specification of position of
atoms and the kind of states

Initial guess of the

wave function

Calculation of the overlap Eq.(2-

21) and core Hamiltonian Calculation of two
Eq.(2-23) electron integrals
Eq.(2-24)

→
Calculation of Eq.(2-

Solve the Roothan-Hall

equations
↑
No
Calculation of Eq.(2-25)

Calculation of Ee Eq.(2-26)

Has energy converged?

← ↓
Correlation corrections
(DFT-GGA) Yes

Calculation of the
band structure and
physical properties
End

Fig.(2-5): A flow chart of the computational procedure for

obtaining band structure and physical properties of CdSe
74
Semiconductors.
Chapter Three
Theoretical
Results and
Discussion

75
 3-1 Introduction
The aim of this work is divided into two subclasses according to the
schematic diagram Fig.(3-1) as following :

Theoretical and experimental

scheme of CdSe nanoparticals

Experimental part
Theoretical part To prepare collidal CdSe
nanocrystals via chemical
reaction method

Gaussian 03 program Structural study

Using Ab-initio DFT Optical study Electrical study
quantum mechanic D.C measurement
To measured
XRD to calculate - activation
Grain size , Applying energy
UV-Visible to scherrer equation -Electrical
Electronic Properties for calculate energy conductivity
G.S.=0.9λ/β′cosθ
core (8,16,54,64) atoms gap , Applying
and surface slab Tauc Equ.
geometry 8 atoms )αhν(=B )hν-Eg)r
Hall Effect to
HOMO and LUMO AFM to study measured
Eg= LUMO-HOMO - surface morphology -concentration
-Grain size and -mobility carrier
Roughness -type of carrier

Ionization potential
Electron affinity

Density of state

Fig.(3-1) Theoretical and Experimental scheme of CdSe Nanoparticals.

76
 3-1-1 Theoretical results and discussion
In the present work Gaussian 03 program has been used including Ab-initio
Density functional theory coupled with large until cell ( LUC) method to
determine the electronic structure and physical properties of CdSe
nanocrystals with different sizes. The work is divided into two parts, core and
surface. Three dimensions (3D) and two dimensions ( 2D ) PBC calculations are
used to simulate the core and oxygenated (001)-(1x 1 ) surface respectively. In
LUC method only the lattice constant is optimized for core part. However, in
the surface part all bond lengths and angle still need to be optimized
because of surface reconstruction.

In core part we chose the number of atoms ( 8, 16, 54 and 64). In

Bravais unit cell chosen part of nanocrystals equal directions in the three
orthogonal coordinates is used which given cubic shapes but in primitive
unit cell parallelogram shape is formed because these primitive unit cell
takes the repeated vectors in non-orthogonal coordinates in all directions.
We need to investigate only one face since other faces are identical to this
facet. This also add another reduction to the calculations efforts. The
oxygenated (001)-(1X 1) CdSe surface is chosen since it is one of the least
reconstructed surfaces. Unlike the core part the bond lengths and lattice
constant are not unique and a variation of geometrical parameters is needed.

In this section we calculate the properties of CdSe nanocrystal for

chosen number of core part ( 8, 16, 54 and 64 ) and surface part for chosen (8)
number of atoms (Cd8Se8O4).

77
3-2 Electronic properties of CdSeNanocrystlasinLUC:
3-2-1 The total energy:
In order to obtain the more stable geometry for CdSe nanocrystals structure
are studied by using Gaussain 03 and Gaussian view program as a complementry
program to show the structure geometry. Figures, (3-2), (3-3) show the total
energy as a function of lattice constant for (8 and 54) atoms core. The results
show that the minimum at the bottom represents the equilibrium lattice constant of
this cell, while the equilibrium lattice constant occurred at a point in which the
attraction forces between the atoms equals to the repulsion forces.

The behavior of total energy as a function of lattice constant is due to the attraction
forces that take place at the large distances between atoms. Increasing the distance
between atoms leads to decrease the total energy. At shorter distances between
atoms, the repulsion forces become dominant and take place to cause the increase
of the total energy.

The fitting of potential curve with polynomial equation give the equilibrium
lattice constant around (0.587,and 0.585)nm respectively. The stability of the
nanocrystals at the equilibrium lattice constant are due to the equality of attraction
and repulsion forces at this point [107].

78
 0.56 0.57 0.58 0.59 0.6 0.61 0.62 0.63
-31150.345
-31150.35
Total energy(a.u.) -31150.355 y = 40.573x2 - 47.731x - 31136

-31150.36
-31150.365
-31150.37
-31150.375
-31150.38
-31150.385
-31150.39
-31150.395

lattice constant (nm)

Fig. (3-2) Total energy versus lattice constant of CdSe

nanocrystals (8)atoms core in LUC.

0.565 0.57 0.575 0.58 0.585 0.59 0.595 0.6 0.605

-210265.6

-210265.62 y = 376.03x2 - 438.46x - 210138

Total energy (a.u)

-210265.64

-210265.66

-210265.68

-210265.7

-210265.72

-210265.74
Lattice constant (nm)

Fig. (3-3) Total energy versus of lattice constant of CdSe nanocrystals (54)
atoms core LUC.

79
 On the other hand, the total energy for core part decreases with increasing
the number of atoms core per LUC as shown in fig. (3-4). On the scale shown in
this figure, the size dependence of the energy is linear.The total energy has a high
sensitivity to the potential energy of the crystal. The potential energy of the crystal
varies with all the a mentioned effects.

0 10 20 30 40 50 60 70
0

-50000
Total energy ( a.u)

-100000

-150000

-200000

-250000

-300000

number of core atoms

Fig. (3-4) Total energy as a function of number of core atoms form CdSe
nanocrystal

3-2-2 The geometric structure

The figures (3-5), (3-6) shows the geometric structure of ( 8 and 54)
atoms core LUC inperiodic boundary conditions, which appears is a multiple of the
Bravais cell, this is a cubic (zinc blende) structure in 8 atoms core ,while appears
is a multiple of the primitive cell, this is a parallelepiped structure in 54 atoms
core [108].

81
 Fig.( 3-5) color online CdSe ( 8) atoms core Cubic
(Bravais multiple Cell ) LUC

Fig. (3-6) Color online CdSe (54) atoms core Parallelepiped

(primitive multiple cell) LUC.

81
3-2-3 lattice constant
Fig.(3-7) shows the relationship between the lattice constant and the number
of core atoms for all studied LUC sizes of CdSe( nc s) core. The lattice constants
decreasing values from 0.587nm for 8 atoms to 0.58 nm for 64 atoms LUC. Also
shows the optimized core lattice constant of the range of nanocrystals between (
1.761- 2.32 nm.) A similar behaviour is observed in previous studies [109].

0.592
Lattice constant (nm)

0.59
0.588
0.586

0.584
0.582
0.58
0.578
0 10 20 30 40 50 60 70

Number of core atoms

Fig.(3-7) lattice constant as a function of number of core atoms

for CdSe nanocrystal.

3-2-4 Cohesive Energy:

The cohesive energy is calculated from the total energy of the LUC.
The large unit cell is composed of (8, 16, 54 and 64) atoms for CdSe(ncs) LUC.
The cohesive energy ECoh is given by :
ECoh  ( ETot / n)  E free  EO
where ETot: is the total energy.
n : is the number of atoms in LUC ( 8, 16, 54 and 64).
EO:is the vibration energy of ground states(zero-point).
EO = (9/8) KB .

82
 where, KB is the Boltzmann constant.
. Is the Debye temperature which equal to 158 K[1]
Efree: is the free atom energy, it means the energy of one atom for
CdSe(ncs). Its value (-3893.5684a.u) from the present work.
where ECd = -5412.8465 a.u and ESe = -2374.2903 a.u

The relation between the cohesive energy and the number of atoms core per LUC
is shown in Fig. (3-8).

0 10 20 30 40 50 60 70
-6.25
Cohesive energy (eV)

-6.3
-6.35
-6.4
-6.45
-6.5
-6.55
-6.6
-6.65

Number of core atoms

Fig. ( 3-8) The cohesive energy as a function of the number of core

atoms for CdSe nanocrystal

In Fig. (3-8) the absolute value of the cohesive energy decreases with
increasing the number of atoms per LUC. The atoms on the particle’s surface
reconstructed to a more stable structure. The calculated cohesive energy is
directly proportional to the value of the total energy. The correct calculated value
of the total energy gives a correct value of the cohesive energy [110] .

83
3- 2-5 Energy Gap:
One of the most important electronic properties of solid is the energy gap. The
energy gap is the difference between the Highest Occupied Molecular Orbital
(HOMO) in the valance band and the Lowest Unoccupied Molecular Orbital
(LUMO) in the conduction band .
The energy gap in (eV) as a function of number of core atoms for all size of
CdSe(ncs) is shown in Fig.(3-9).

1.78
1.775
1.77
Energy gap (eV)

1.765
1.76
1.755
1.75
1.745
1.74
1.735
1.73
1.725
0 10 20 30 40 50 60 70

Number of core atoms

Fig. ( 3-9) The energy gap as a function of number of core atoms of CdSe
nanocrystals LUC.

In the above figure ( 3-9 ) we shown the energy gap decrease with number of core
atoms in ( 16, 64 ), but increase with number of core atoms in ( 8, 54 ) .That
means the relationship is non-linearly between the energy gap and number of core
atoms, The energy gap is between ( 1.73 - 1.77 eV ) at the minimum value of
lattice constant , and it obtain with the other values in theoretical and experimental.
This is a clear indication of geometry effects on electronic structure of
nanocrystals. [111].

84
3-2-6 Valence and Conduction Band Width:
We calculated valence and conduction band width using Gaussian(03)
program. Valence band width is the difference between the highest occupied
molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO). And
conduction band width is the difference between the last virtual value and the first
virtual value.
The valence and conduction band width for the CdSe (nc s) core for different size
is shown in Fig. (3-10);the valence bandwidth is increases with increasing number
of atoms core LUC, because of the geometry effects on electronic structure of
nanocrystals; While we note conduction band width increases with increasing
number of atoms LUC, reaching to 16 atoms, but at 54 atoms C.B. width is
decreases to 6.040ev and after that it increasing reaching to 64 atoms. Our studies
are in good agreement with previous studies [111, 112].

.
30
V.B width & C.B width ( eV )

25

20

15
V.B
C.B
10

0
0 10 20 30 40 50 60 70
Number of core atoms

Fig. ( 3-10) Valence band width and Conduction band width as a

function of number of core atoms for CdSe nanocrystal LUC

3-2-7 Ionicity:
The ionicity charge is calculated as a function of number of atoms as
shown in figure (3-11). The ionicity decrease with increasing number of atoms

85
core part. However, the ionic charge of cadmium atoms is equal to the ionic charge
of selenium atoms and the net charge is equal to zero. This property was also noted
previously in LUC calculations for other nanocrystals [105].

0.46
Ionicity ( arbitrary unit )

0.44
0.42
0.4
0.38
0.36
0.34
0.32
0.3
0 10 20 30 40 50 60 70
Number of core atoms

Fig.( 3-11) The Atomic Ionicity as a function of number of core atoms

of CdSe nanocrystals LUC.

3-2-8 HOMO (Ionization potential ) and LUMO (Electron affinity) :

HOMO is the highest occupied molecular orbital, while LUMO is the

lowest unoccupied molecular orbital for all size of CdSe nc satoms core as shown
in Fig.(3-12).
Where:
HOMO =| the last occ.| = is the Ionization potential.
LUMO = | the first virt. | = is the Electron affinity.

86
 16

14
HOMO & LUMO ( eV )

12

10

4 HOMO
2 LUMO

0
0 10 20 30 40 50 60 70

Number of core atoms

Fig.(3-12 ) HOMO & LUMO as a function of number of core atoms

for CdSe Nanocrystals .

The fig.(3-12) shows the variation of highest-occupied molecular orbital

energy (HOMO) and lowest –unoccupied molecular orbital energy (LUMO) as the
core of number of atoms grows up in size and changes its shape. This curve
fluctuates strongly because of the change in size and shape that produces different
surface that have different properties[107] .

3-2-9 Density of states:

In physics, two or more different physical states are said to be degenerate if
they are all at the same energy level. Physical states differ if and only if they are
linearly independent. An energy level is said to be degenerate if it contain two or
more different states. The number of different states at a particular energy is called
the levels degeneracy.

87
The highest density of states of CdSe nanocrystals(ncs) as a function of the energy
levels for lowest energy lattice constant were calculated for ( 8, 16, 54 and 64)
atoms for core part.
In figures (3-13), (3-14), (3-15) and (3-16) are show the at the edges of the
conduction and valence bands are generally less degenerate than the states at the
middle of these bands. One can see from the core part that there are higher
degeneracy states. This result reflects the high symmetry for these structures which
agrees with the results of the total energy and band gap.

7
DOS 8
atoms
6
Density of States/ eVatom

5
Eg=1.77 e.V
4

0
-30 -20 -10 0 10 20

Energy (e.V)
Fig. (3-13) The density of states as a function of energy levels for CdSe
nanocrystals ( 8) atoms core in LUC. Valence band are shown with bold
lines, while conduction band are shown with ordinary lines. The energy gap is
shown between the two bands ( Eg=1.77 eV).

88
Fig.(3-14) The density 0f states as a function of the energy levels for 16 atoms
core LUC. Valence band are shown with bold lines, while conduction band
are shown with ordinary lines. The energy gap is shown between the two
bands (Eg=5.74ev).

DOS 54 atoms

60
Density of state / eVatom

50
Eg=1.76 ev
40

30

20

10

0
-15 -10 -5 0 5 10 15 20 25
Energy (ev)

Fig.(3-15) The density of states as a function of the energy levels for 54 atoms
core LUC. Valence band are shown with bold lines, while conduction band are
shown with ordinary lines. The energy gap is shown between the two bands
(Eg=1.76eV).

89
 DOS 64 atoms

60
Density of state / eV atom

50

40
Eg= 1.74 eV

30

20

10

0
-25 -20 -15 -10 -5 0 5 10 15 20
Energy ( ev)

Fig. (3-16)The density of states as a function of the energy levels for 64 atoms
core LUC. Valence band are shown with bold lines, while conduction band
are shown with blue lines. The energy gap is shown between the two bands
(Eg=1.74eV)

In Fig.(3-17), the density of state as a function of the energy levels for

number of core atoms for CdSeis shown that the density of states increase with
increasing the number of atoms core .

91
 60
Density of states/ eV atom

50
40
30
20
10
0
0 10 20 30 40 50 60 70

NO. of core atoms

Fig.( 3- 17) The density of states as a function of number of core

atoms for CdSe nanocrystal

3-2-10 The Comprehensive Electronic Structure:

The electronic structure properties of CdSe(ncs) are calculated according to
the Gaussian 03 program. These properties are listed in Table (3-1) which shows
the all calculation , such as E total ,E nuclear , Eg, electron affinity, ionization
potential, ionicity, conduction and valence band width and cohesive energy for
each number of atoms core for core part.

91
Table(3-1): Electronic Structure Properties of CdSe Nanocrystals for (8 , 16 , 54 , 64 ) core atoms LUC

Alloy Lattice E total E nuclear Eg Electron Ionization Iconicity Fermi Conduction Valance Cohesive
compound constant repulsion affinity potential a.u level band width band Energy
nm a.u a.u eV eV eV eV eV width eV
eV
8CdSe atoms 0.58 -31150.3881 6573.1241 1.88 7.447 5.5590 0.4339 0.944 9.0579 24.4095 - 0.2301
0.585 -31150.3909 6516.9435 1.80 7.248 5.440 0.436 0.904 8.9403 24.2656 - 0.2304
Minimum 0.587 -31150.3913 6499.6275 1.77 7.171 5.397 0.437 0.887 8.9199 24.2315 -0.2305
0.59 -31151.3913 6466.6474 1.72 7.159 5.336 0.438 1.861 8.8446 24.1347 - 0.2305
0.595 -31151.3894 6412.1726 1.64 6.857 5.211 0.441 1.823 8.7436 24.1121 - 0.2302
0.60 -31151.3854 6354.0199 1.57 6.664 5.194 0.443 1.785 8.6135 23.8566 - 0.2297

16CdSe atoms 0.575 -62300.771 24283.1697 1.95 4.614 2.664 0.420 0.975 9.20 24.653 -0.2297
0.58 -62300.7824 24072.2146 1.88 15.194 13.313 0.4239 0.94 9.053 24.472 -0.2305
Minimum 0.59 62300.7887- 23664.2110 1.73 14.734 13.002 0.430 0.86 8.82 24.167 -0.2308
0.60 62300.7759- 23269.8074 1.57 14.244 12.666 0.437 0.78 8.6 23.88 -0.23
0.61 62300.7466- 22912.7356 1.42 13.721 12.297 0.444 0.71 8.412 23.661 -1.2282

54 CdSe atoms 0.57 -210265.6619 203568.3530 1.90 14.818 12.917 o.3547 0.95 8.254 25.365 -0.240

0.575 -210265.6996 201790.7758 1.84 4.475 2.633 0.358 0.920 8.167 25.208 -0.241
Minimum 0.58 -210265.721 200033.8916 1.76 14.452 12.683 0.362 0.884 8.032 25..01 -0.2412
0.59 210265.7072- 196589.3760 1.62 3.959 2.334 0.371 0.812 7.97 24.805 -0.240
0.60 -210265.6162 192992.3829 1.48 14.640 13.155 0.379 0.742 9.05 25.165 -0.239

64 CdSe atoms 0.57 -249203.8418 277402.8304 1.88 7.406 5.520 0.343 0.94 9.412 25.434 -0.2416

Minimum 0.58 -249203.903 272620.0230 1.74 7.047 5.299 0.352 0.87 9.137 25.089 -0.2425
0.587 -249203.8957 269373.4939 1.64 6.795 5.147 0.3583 0.82 8.959 24.861 -0.2425
0.59 -249203.8801 267995.8254 1.60 6.684 5.079 0.3609 0.80 8.900 24.767 -0.2422
0.6 -249203.7842 263532.6889 1.45 6.325 4.866 0.3703 0.72 8.656 24.460 -0.2400

92
3-3 Oxidization Surface part of the Cd8Se804:
In order to complete the view of the electronic structure of CdSe
nanocrystals, the oxidized surface part of CdSe is investigated. Slab geometry
of the stoichiometry Cd8Se8O4 is used for this purpose.
Figure (3-18) shows the total energy for CdSe surface as a function of lattice
constant for the stoichiometry (Cd8Se8O4) atoms. The optimized bond length
(Cd=O) is (1.71 A˚) while that of ( Se=O) is (1.67 A˚). However these values in
other studies are ( 2.0A˚) for ( Cd=O) and (1.53A˚) for (Se=O) .
The optimized average surface lattice constant is (5.85A˚). While its value for 8
atoms for core part (5.87A˚) . The energy gap of this stoichiometry is (0.02eV),
while in core part is equal (1.77 eV).
From comparing the energy gap of LUC of core with the energy gap of oxygenated
(001)-(1×1) surface, we can note that the energy gap at the surface is much less
than that at the core. As a consequence, the energy gap is controlled by the surface
of nanocrystals.
But we are unable to calculate the bond length of 16, 54 and 64 surface
atoms because of the long time needed and faster computer ( more than one
day for each point ).

93
 0.582 0.583 0.584 0.585 0.586 0.587 0.588 0.589
-62596.62

-62596.64

-62596.66

-62596.68
Total energy (a.u)

-62596.7

-62596.72

-62596.74

-62596.76

-62596.78

-62596.8
Lattice constant (nm)

Fig. (3-18) Total energy for 8 core atoms oxygenated (001)-(1×1) CdSe
surface as a function of lattice constant.

The atomic positions of the stoichiometry ( Cd8Se8O4 ) atoms is drawn using

Gaussian view. The oxygenated (001)-(1×1) CdSe surface similar to the Ketone
configuration is investigated to obtain the total electronic structure of CdSe (nc s)
with (001)-(1×1) facets.

Figure (3- 19) shows the atomic position of (Cd8Se8O4 ) stoichiometry atoms
slab calculations of oxygenated a2 area surface CdSe layers.

94
Fig.(3-19) Atomic position of Cd8Se8O4 stoichiometry atoms slab calculations
of oxygenated a2 area surface CdSe layers.

95
 The Cd and Se atoms take the charges +0.331and - 0.306 arbitrary unit
(a.u), respectively, in an eight-atom core. At the oxygenated surface slab.
Fig. (3-20) shows the same negative and positive charges are assigned to Cd and
Se atoms, respectively, and the atomic charge of oxygenated (001)-(1×1) surface
calculated for stoichiometry Cd8Se8O4 atoms as a function of layers distance.

0.5
Cd Cd Cd
Cd
0.4

0.3
Atomic charge( Arbitrary unit )

0.2

0.1

0
0 2 4 6 8 Se 10 12
-0.1

-0.2
o
-0.3 o
Se
-0.4 Se Se

-0.5
Layer number

Fig.(3-20) Ionic charge of oxygenated (001)-(1x1)surface slab for 8 atom LUC

as a function of layer depth.

Figure (3-21) shows the density of state for 8 atoms for surface part, it shows
that a low density of state compared with core part. This lowering density of state
in surface part caused by the broken symmetry at the surface discontinuity, and the
existing of oxygen atoms leads to varying the bond length and lattice constant.

96
 Eg =0.02
eV

Fig.(3-21) The Density of states of 8 atoms for surface oxygenated (001)-(1×1)

slab having a2 area. Valance band are shown with bold lines, while conduction
band are shown with ordinary lines. The energy gap is shown between the two
bands which have energy ((-2.775 - -2.802 e.V).

For the surface part, one can see that the surface density of states of
oxygenated (001)-(1x1) slab have a dominant role on the energy levels. The
splitting of energy level does not affect the number of degenerate state only but
also the conduction band widths, which are wider in the surface part[70].The
splitting of states and additional states have an effect on the band gap.
The comparison shows that the energy gap and valence band decrease in the
surface part, while the conduction band width increases . This is due to the
broken symmetry at the surface discontinuity and existence of new kind of atoms
(oxygen atoms) [110].
In Table (3-2).shows the electronic structure properties of 8 atoms of CdSe-
oxidized surface nanocrystals.

97
 Table (3-2): Electronic Structure Properties of CdSe - Oxidization Atoms Nanocrystals

Alloy Lattice E total E nuclear Eg Electron Ionization Ionicity Fermi Conduction Valance Cohesive
compound constant repulsion affinity potential (a.u) level band width band Energy
nm a.u a.u eV eV eV eV eV width (eV)
eV

Cd8Se8O4 0.583 -62596.6394 24412.5946 0.108 2.721 2.829 0.3467 0.054 13.823 20.870 -5.779

0.584 -62596.7397 24370.9231 0.0272 2.800 2.804 0.3896 0.013 13.877 20.860 -5.915
Minimum 0.585 -62596.7861 24356.674 0.027 2.775 2.802 0.3645 0.013 13.87 20.840 -5.980

0.5875 -62596.7836 24246.4664 0.054 2.748 2.802 0.3602 0.027 13.795 20.843 -5.975
0.588 -62596.7257 24210.120 0.022 2.775 2.775 0.3956 0.011 13.823 20.870 -5.896

98
 Chapter Four

Experimental part

99
4-1 Introduction
This chapter presents the description of the method implemented in our
research for the preparation of CdSe nanoparticles. The testing for CdSe
nanoparticles is made by studying the optical properties from the measurements of
the absorbance spectrum in order to calculate the energy gap of the formed
quantum dots. Then the phase structure and morphology and grain size are
measured by X-ray diffraction and AFM as well as D.C measurement and Hall
effect to study the conductivity , thermal activation energy and types of carrier.

4-2 System of Colloidal CdSe Nanoparticles Preparation

The cadmium selenide CdSe nanoparicles were prepared as a colloidal by
chemical reaction of sodium selenosulfide (Na2SeSO3) and cadmium chloride
CdCl2 with 0.1gm gelatin of 40mM at different molar ratio (1:1, 1:2, 1:4) and
agitated continuously at temperature until the CdSe nanoparticles were formed.
The resulting solutions were obtained by adding ethanol followed by
centrifugation as shown in the following equation:

CdCl2  Na2 SeSo3  2H 2O  CdSe  2 NaCl  2H 2O  SO3 

nanoparticles

The Cd+2:Se-2 ratios indicated are the molar ratios of (CdCl2) solution to
(Na2SeSO3) solution. During the experiment the concentration of Cd+2 and Se-2
ions in the final solution is adjusted by changing the volume of CdCl2 solution
while holding the volume of Na2SeSO3 solution is constant.

4-3 Preparation Solutions

Sodium selenosulfate (Na2SeSO3) was chosen as the selenium source.
Na2SeSO3 solution 20mM was prepared by mixtuing 2mmol selenium powder and

111
4mmol Na2SO3 in 100ml dionized water at ( 353 ok ) for three hours and final
solution was adjusted to 20mM.

4-4 X-Ray Diffraction of CdSe Nanocrystals

The X-ray diffraction patterns of the CdSe nanoparticles samples are obtained. By
(2600 XRD , CHIMATZA ,Japan) . And to calculate the interplaner distance
according to Bragg equation as follows:
2d sin   n ........................................(4-1)

In the other hand the X-ray diffraction 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 [88].
D= 0.9 λ ⁄ β′ cos θ ...................(4-2)

where:
D is the quantum dot size.
λ is the wavelength for X-ray source ( X-ray source is CuKα with
λ=1.5406Å).
β′ is the full width at half maximum (FWHM).
θ is the diffraction angle.

4-5 Optical Properties

The optical properties of the prepared CdSe nanoprticles has been investigated .

4-5-1 Optical Constants

The optical constants are very important parameters because they describe
the optical behavior of the materials. The absorption coefficient of the material is a
very strong function of the photon energy and band gap energy. Absorption
coefficient represents the attenuation that occurs in incident radiation intensity on

111
the material for unit thickness, and the main reason for this attenuation is attributed
to the absorption processes [16, 24]. Optical constants included refractive index
(n), extinction coefficient (k′), and real (εr) and imaginary parts (εi) of dielectric
constant.

The complex refractive index (nc) is defined as [108]:

nc  n  ik ………………………………………... ( 4-3)

And it is related to the velocity of propagation (v), and light velocity (c) by:

v =c/nc ……………………………………...... (4-4)

The refractive index value can be calculated from the formula [109]:

1
 4R 2  2 (R  1)
n    k  
 ………………........(4-5)
 (R  1)
2
 (R  1)

Where R is the reflectance, and can be expressed by the relation [108]:

(n  1) 2  k  2
R ………………………............. (4-6)
(n  1) 2  k  2

The extinction coefficient, which is related to the exponential decay of the

wave as it passes through the medium, is defined as [110]:

αλ
k  …………………………........................(4-7)
4π

112
Where  is the wavelength of the incident radiation and the absorption coefficient
() is given by [30]:
A
α  2.303 .................................... (4-8)
t

where A is the absorptance and t is the sample thickness. The real and imaginary
part of dielectric constant (r ,i ) respectively can be calculated by using the
following equations [105]:

(n  ik ) 2  ε r  iε i ……............................ (4-9)

where
εr  n 2  k2 ……………………………. (4-10)

and εi  2nk …………………………....(4-11)

4-5-2 The optical Energy Gap Calculation

The UV-visible absorption spectrum of semiconductors is mainly a particle
size dependent , which give size to calculate the mean nanoparticles size . The
optical energy gap (Eg) of the semiconductor is calculated from Tauc relation can
be used to estimate the nanoparticles size as follows:

h  (h  Eg )r …………........(4-12)

where B is constant , r is a parameter that has different values (1/2,3/2) for direct
allowed and forbidden transitions respectively and (2,3) for indirect allowed and
forbidden transitions respectively .

113
Then the crystal size or nanoparticle size (diameter) was calculated from energy
gap using equation as follow :
 2 2
E (eV )  …………………....................(4-13)
2m  r 2
E  E gdot  E gbulk ………………………........(4-14)

where: Eg dot is quantum dot energy band gap Eg bulk is bulk energy
band gap.
m* is effective mass for crystal
r is radius of quantum dot

4-6 Absorption Spectrophotometer

The ultra-violet visible spectra of the samples was measured using OPTMA
SP-3000 UV-Vis Spectrophotometer supply by optima company . This
spectrophotometer covers the UV , visible and NIR range from (200-1200)nm as
shown in Fig.(4-1). The scanning range of the CdSe nanoparticles absorbtion was
(200-1000)nm using glass substrate as a reference sample .

Figure (4-1) : The OPTMA SP-3000 UV-Vis spectrophotometer

114
4-7 Atomic Force Microscope (AFM)

Atomic Force Microscope studies was recorded by using CSPM AA 0333

AFM supply by Angstrom Company as shown in figure )4-2( to determine the
particles dimensions range of the prepared CdSe and their statistical distribution.

Fig.(4-2) AFM (Atomic Force Microscope)

4- 8 Intrinsic Mobility

The mobility is the magnitude of the drift velocity of a charge carrier per
unit electric field is [113] :

μ = vd / E ..........................................(4- 15)

The electrical conductivity is the sum of the electron and hole contributions:

σ = (n n n μ℮ + p n μ h ) .......................(4-16)

where n and p are the concentrations of electrons and holes.

σ= n n μ .............................................( 4-17)
μ=σ RH .............................................(4-18)

115
and the Resistively is :

ρ = 1/ σ ) Ω.cm)‾ˡ ................................(4-19)

and the resistance as follow :

R′ = ρL /Aa ................................................. (4-20)

where: L is the distance between two electrodes , and (Aa) is the area for thin
film.

The experimental setup to measure the D.C. Conductivity is shown

in figure ( 4-3).

Fig. (4-3): The Experimental Setup to measure the D.C.

Conductivity.

116
 Chapter Five

Experimental Results
and Discussion

117
 Experimental Results and Discussion

5-1 Introduction
This chapter includes the results and the analysis of the experimental
measurements of the CdSe nanocrystals.
The results include the UV-Visible optical properties, X-ray diffraction and
Atomic Force Microscope (AFM) for surface morphology as well as DC.
conductivity and Hall Effect of the CdSe nanocrystals, which were prepared as a
colloidal by the chemical reaction method.

5-2 X-Ray Diffraction of CdSe Nanoparticles

The X-ray diffraction patterns of the CdSe nanoparticles samples were
obtained. Fig.(5-1) XRD patterns of three CdSe thin films obtained for three
different Se concentrations ( 1:1 , 1:2 and 1:4 ) respectively.

The pattern shows that CdSe is polycrystalline with zinc-blende structure

have two peaks centered around 26o for (111) plane where the other peak is
centered around 44o for plane (220). The boarding of a parent X-ray diffraction at
full width at half maximum indicate that CdSe is in nano-dimension and the grain
size is found to be about 5nm by using scherrer relation (4-2) for films oriented
preferentially (111) plane with different Se concentrations.

118
 2θ
Fig.(5-1) X-ray diffraction pattern of CdSe nanoparticles at different Se
concentrations

The X-ray peaks and their band width are illustrated in Table (5-1). The listed table
contains the corresponding grain size of the prepared nanoparticles measured
according to the scherrer equation .

119
Table (5-1) The different concentrations of CdSe Miller indices , intensity , 2θ
, FWHM , interplaner distance (d), grain size and crystal structure .

Cd:Se Hkl I/Io 2θ (FWHM) d (nm) Grain size Crystal

concentratio (degree) (nm) structure
n
1:1 111 100 26.3112 1.9 0.33845 5.044703 zinc-blende
1:2 111 100 25.9493 2 0.343088 4.341128 zinc-blende
1:4 111 100 25.8058 2.18 0.344763 3.859279 zinc-blende

X-ray diffraction measurement shows that the average particle size decrease with
CdSe nanoparticles of Se ratio concentration increase.

5-3 Optical Properties

The optical properties of the prepared CdSe nanoprticles has been investigated .

5-3-1 Optical Constants

The properties include the UV –Visible absorption , transmission spectra of the
product is an efficient technique to monitor the optical properties of quantum-
sized particles. The absorptance and transmitance spectra of the CdSe
nanoparticles are shown in Figs.(5-2) and (5-3) respectively. These figures show
that the absorbance will be increased with increasing Se concentration while the
transmitance will be decreased correspondingly.

111
Fig.(5-2) UV-Visible absorption spectrum of CdSe nanoparticles at different
Se concentrations a)1:1 b)1:2 c)1:4

111
Fig.(5-3) Transmittance spectrum of CdSe nanoparticles at different Se
concentrations: a)1:1 b)1:2 c)1:4

112
5-3-2 The optical energy gap calculation
A plot of (h ) 2 versus h shows intermediate linear region , the
extrapolation of the linear part can be used to calculate the Eg from intersect with
x- axis as shown in Fig.(5-4) . The resultant values of Eg for CdSe at different
ratio molarity of Se concentration is found to be varied from (1.8- 2.5) eV .
respectively.

Fig.(5-4) versus with hν for CdSe nanoparticles

at different Se concentrations: a)1:1 , b)1:2, c)1:4

The resultant values of Eg for CdSe at different molar ratio of Se concentrations

and others optical parameters are list in Table (5-2).

113
Table (5-2) Optical parameters like absorption coefficient α , extension
coefficient k′ , refractive index n , real and imaginary dielectric constant
( r ,i ) and energy gap Eg , Absorbance (A), Transmittance (T) and
Reflectance ( R ) at (λ=650nm) .

Molar α X104 K′ n r i Eg Particle A T R

-1
ratio of cm (eV) size (nm)
CdSe
1:1 126.96 6.57 7.92 19.56 104.06 1.8 57.8 0.5 0.244 0.256
1:2 36.54 1.89 3.01 5.48 11.37 2.3 56 0.164 0.785 0.051
1:4 28.277 1.46 2.50 4.11 7.3 2.5 45 ..126 0.896 -0.022

5-4 Atomic force microscope (AFM)

The atomic force microscope (AFM) is one of a family of scanning proble
microscopes, The AFM images of the surface morphology of the CdSe
nanoparticles films gives a good indicator for formation of the CdSe nanoparticles.
The average particle size and roughness of CdSe nanoparticles with different Se
concentration determined from AFM are shown in Table (5-3) and figures (5-5)
and Fig.(5-6) respectively .

114
 Table (5-3) Average particles size, Grain size, and Roughness of CdSe

with different Se concentrations

CdSe Average particle size (nm) Grain size (nm) Roughness (nm) (AFM)
(AFM)
(Scherrar eq.)

1:1 132 5.044703 0.897

1:2 91 4.341128 1.06

1:4 81 3.859279 1.09

AFM measurement shows that the average particle size decrease with CdSe
nanocrystal of Se ratio concentration increase , while the roughness increase.

The main difference between X-ray diffraction and AFM methods to measured
grain size, that in X-ray using scherrar equation with very low accuracy main while
in AFM the measurement is indirectly.

115
 a

Fig.(5-5) The AFM image of the surface morphology of the CdSe

nanoparticles films at different Se concentrations a)1:1 b)1:2 c)1:4

116
The results are obtained from AFM of CdSe nanoparticles with different Se
concentrations in 2D and histogram as a function of the average particle size as
shown in Fig.(5-6) :

(a)

(b)

(c)

Fig.(5-6) AFM of CdSe nanoparticles in 2D and histogram as a function of the

grain size at different Se concentrations , a)1:1 b)1:2 c)1: c)1:4
117
5-5 D.C conductivity and Hall Effect measurements
In order to study conductivity mechanisms, it is convenient to plot logarithm
of the conductivity (ln σ) as a function of 1000/T for CdSe thin films in the range
(303 – 453)K at ratio (1:1) of as shown in Fig. ( 5-7 ).

It is seen that resistivity decreases with temperature, indicating semi conducting

nature of films.

The thermal activation energy was calculated using the relation

ρ = ρο exp(Ea/ KB T) (5-1 )

where: ρ is resistivity at temperature T, ρο is a constant (resisitivity at 0 ºK) ,

−5
KB is Boltzmann constant (8.62 × 10 eV/K) and Ea is the activation energy
required for conduction .

Also It is clear from the figure that there are two transport mechanisms,
giving rise to two activation energies Ea1 and Ea2.
At higher temperature range (393 – 453) K the value of ( Ea1 is 0.7) eV, the
conduction mechanism is due to carrier excited into the extended states beyond the
mobility edge and at lower temperature range (303 – 388) K; the value of ( Ea2 is
0.04) eV, the conduction mechanism is due to carrier excited into localized states
at the edge of the band.

118
 -8

-10

-12

Ln 
-14

-16
2 2.5 3 3.5
1000/T(K)-1

Figure (5-7) Ln σ versus 1000/T for CdSe thin films at ratio of (1:1) .

These observations may be due to size effects that are arising because of quantum
confinement of charge carriers within the particles.

From Hall Effect , It is observed that the type of concentration is n-type,

Conductivity , Hall coefficient and mobility have been calculated as shown in
Table (5-4).
Table (5-4) Values of  R.T, RH, nH , µ and Type of Conduction for CdSe
thin film at concentration (1:1).

 R.T RH nH µ
Type
CdSe (.cm)-1 (cm3/c) (cm)-3 (cm2/V.s)
1:1 1.15x10-5 -4.66x107 1.34x1011 535.9 n-type

119
5-6 Conclusion
From the present work, the main conclusion summarized are:
1- The lattice constant of II-VI zinc-blende CdSe nanocrystal core decreased with
increasing the number of core atoms in the LUC .
2- The energy gap decreased with increasing the number of core atoms while the
conduction band increase as CdSe nanocrystal LUC size increases.
3- The cohesive energy and ionicity were decreased with number of core atoms
increase.
4-The density of states of the core part is higher than that of the surface part. This
reflects the high symmetry and equal bond lengths and angles in perfect CdSe
nanocrystals structure.
5-Colloidal CdSe nanoparticles can be synthesized by chemical method with zinc-
blende nanostructure.
6-The average particle size was reduced by increasing Se ratio while the roughness
was increased.
7- The absorption peak spectrum was obtained in visible region and shift towards
lower wavelength by increasing Se ratio. This indicates of decreasing the grain size
and increased in effective band gap.
8-For smaller average size , there is larger distribution of nanocrystalline sizes,
causing boarding of XRD peak. The average particle size decrease with increase
Se ratio as indicate by AFM measurements.
9- The D.C measurement indicate that the activation energy of CdSe nano crystal
at high temperature is approximately half of energy gap with n-type
semiconductor.

121
5-7 Suggestions

We suggest the following studies as a future works:

1- Using the same approximation of density functional theory to study the
electronic properties of ternary CdSeXTe1-X alloying composition.

2- Fabrication of CdSe nanocrystal with organic layer as a window for solar

cell device .

121
References
[1] H. E. Jackson, " Probing Electronic Vibronic States in CdTe
Self- Assembled Quantum Dots " Ph.D. Thesis, University of
Cincinnati, (2006).
[2] J. M. Martinez-Duart, R. J. Martin-Palama and F. Agullo-Ruedo,
" Nanotechnology for Microelectronics and optoelectronics " ,
Elesvier B. V. , AE Amsterdam, The Netherlands, (2006).
[3] J. Zhang, " Control of Electronic Coupling and Optical Properties
in Quantum Dot Solids " Ph.D. Thesis, University of Munchen ,
China ,(2010).
[4] V. S. Varavin , V. V. Vasiliew , S. A. Dvoretsky , "HgCdTe
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