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STUDY OF THE ELECTRONIC, OPTICAL AND

STRUCTURAL PROPERTIES OF LEAD-


CHALCOGENIDES PbX (X=S, Se, Te)

THESIS

Submitted to the
Banasthali Vidyapith
FOR THE DEGREE OF
Doctor of Philosophy
(PHYSICS)

By:
Pooja Bhambhani
Department of Physics
Banasthali University
Banasthali-304022

Under the Supervision of

Dr. Ghanshyam Sharma


Associate Professor
Department of Pure & Applied Physics
University of Kota, Kota (India)

December, 2013
Department of Pure & Applied Physics
University of Kota, Kota
Maharao Bhim Singh Marg, Near Kabir Circle, Kota

-----------------------------------------------------------------------------
Date:

SUPERVISOR’S CERTIFICATE

This is to certify that the thesis entitled “Study of the electronic, optical and
structural properties of lead-chalcogenides PbX (X=S, Se, Te)” describes
the original work done by Ms. Pooja Bhambhani under my supervision for the
degree of Doctor of Philosophy of the Banasthali Vidyapith, Banasthali.
Ms. Pooja Bhambhani has also fulfilled the required formalities as per
University norms.

(Dr. Ghanshyam Sharma)


Associate Professor

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ACKNOWLEDGEMENTS
The work presented in this thesis would not have been possible without my close
association with many people who were always there when I needed them the
most. I take this opportunity to acknowledge them and extend my sincere
gratitude for helping me make this Ph.D. thesis a possibility.
First of all, I would like to express my sincerest gratitude to my supervisior,
Dr. Ghanshyam Sharma, Associate Professor, Department of Pure & Applied Physics,
University of Kota for his supervision, knowledge, patience, inspiration, advice and
invaluable guidance during the period of study. His constant guidance, cooperation
and support have always kept me going ahead. I feel privileged to be associated with
him.
I wish to express my sincere thanks to Prof. Aditya Shastri, Vice-Chancellor,
Banasthali Vidyapith for providing all the computational and experimental facilities to
carry out this work.
It is with immense gratitude that I acknowledge the support and motivation of
Dr. D.R. Phalaswal, Head, Department of Physics, Banasthali Vidyapith.
It is great pleasure to thank my all colleagues namely, Dr. Vimal Vyas, Dr.
Vibhav Sharaswat, Dr. Amarjeet Singh, Dr. Sarita Kumari, Dr. Saral Kumar Gupta,
Dr. Pravez Ahmed Alvi, Dr. Ajay Singh Verma and Ms. Sheetal Sharma.
I owe my deepest gratitude to Dr. Dinesh Kumar, Associate professor,
Department of Chemistry, Banasthali Vidyapith for his support, invaluable discussions
and constructive suggestions.
My special thanks go to my coworker Dr. Neha Munjal for her precious
support.
I would also like to extend my huge warm thanks to my friends namely,
Ms. Vibha Kapoor and Ms. Chilka Sharma for their kind help and moral support. I am
greatly indebted to Mrs. Neha purohit for always being there for me. Their
contributions cannot be adequately acknowledged.
I would like to thank technical staff members of Department of Physics and
Chemistry, Banasthali Vidyapith for their support in their respective roles.
I would like to acknowledge all the teachers who taught me since my
childhood. I would not have been here without their guidance, blessing and support.

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I would also like to extend my huge warm thanks to my parents. I don’t find
proper words to express my gratitude towards them. It is their encouragement and
support from the very beginning of my life that made it possible for me to reach this
stage. My thanks equally go to my parents-in-law for their timely support. Also,
special thanks to my sisters, for their endless love and care.
Above all, I express my deepest gratitude to my husband, Mr. Bharat Goklani
for his personal support and great patience at all time. This thesis would have never
been possible without him. His continuous support in pursuing my study is invaluable
to me. Words are short to express my deep sense of love towards my daughter,
Bhoomi. Her innocent face and waiting eyes always encourage me to accomplish my
work timely. I would dedicate this thesis to both of them.

Pooja Bhambhani

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SUMMARY

Title: Study of the electronic, optical and structural properties of lead-


chalcogenides PbX ( X = S, Se and Te )
Lead-chalcogenides are some promising semiconductor materials used for
photovoltaics due to their fascinating properties like high carrier mobility, high
dielectric constant and narrow band gap. These semiconductor materials
crystallize in the rocksalt structure at ambient conditions. These materials can
also be used in non-linear optical devices and detectors because of their very
unusual electronic, optical and structural properties. The lead chalcogenides
PbX (with X=S, Se, Te) are of great importance for infrared detection and
lasing devices and furthermore find applications as thermoelectric materials as
window coatings and in solar-energy panels.
In the past decades, nanoscience and nanotechnology have been making
significant progress, and their effects on every field have been acknowledged in
the world. The nanomaterials have attracted enormous attention due to their
size-dependent unique mechanical, physical and chemical properties. Among
them, one dimensional semiconductor nanostructures (such as nanowires,
nanorods and nanotubes) are promising candidates for technological nanoscale
electronic, optoelectronic and photonic applications. Solution-based chemical
synthesis of semiconductor nanostructures has allowed tremendous flexibility
in crystal morphology.
The inherent size dependence of the nanocrystal properties is the result
of quantum confinement. Quantum size effect occurs when the nanostructures
become smaller than a fundamental scale, which is determined by the exciton
Bohr radius. IV-VI materials offer unique access to the regime of extreme
quantum confinement because of their relatively large Bohr radii. Due to large
Bohr radii, strong quantum confinement in IV-VI can be achieved in relatively
large structures, consequently, band gap of IV-VI semiconductors can be easily
tuned by changing their sizes, and hence these materials can be easily used in
optoelectronic devices.

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This thesis includes seven chapters. A brief introduction of IV-VI
semiconductor materials and review of literature allied to the present work are
summarized in the first chapter “Introduction”.
The second chapter “Theoretical and experimental details” presents
an overview of CRYSTAL code based on LCAO method and details of
synthesis of PbS micro- and nano-crystals and characterization techniques.
The remaining chapters include the theoretical as well as experimental
work done on lead-chalcogenides. The next three chapters (3 to 5) deal with the
theoretical work on binary and ternary lead-chalcogenides. In the sixth chapter,
synthesis and characterization of PbS crystals of different sizes are reported.
The third chapter “Structural properties of PbX (X=S, Se and Te)”
describes ground state structural parameters like lattice parameter (a), bulk
modulus (B0), its pressure derivatives (B 0') and cohesive energy (Ecoh) for PbX
compounds in B1, B27 and B2 phases. These parameters have been computed
using GGA and LDA approximations and compared with previously reported
theoretical and experimental data. Along with these structural properties, the
phase transition pressures of lead-chalcogenides from stable phase to
intermediate phase and from intermediate phase to high pressure phase have
also been investigated. The problem of intermediate phase of lead-
chalcogenides has also been tried to be resolved. The intermediate phase of
PbX between B1 and B2 phases has been found to be FeB type (B27, Pnma)
phase.
The fourth chapter “Pressure dependent electronic and optical
properties of lead chalcogenides” describes the electronic and optical
properties of PbX (X=S, Se and Te) compounds. The pressure dependency of
band gap and dielectric constant of PbX have been investigated. The effect of
pressure on covalent nature of PbX has also been observed. The anisotropies in
momentum density also discussed in this chapter.
The fifth chapter “Structural and electronic properties of doped lead-
chalcogenides” deals with the study of structural and electronic properties of
the ternary alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex (x=0, 0.25, 0.50, 0.75 and

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1). The effect of concentration of doping on structural parameters like lattice
constant and bulk modulus has been emphasized. The variation in band gap of
doped lead-chalcogenides with concentration of doping has been studied. The
calculated structural and electronic parameters have been compared with the
previously reported experimental and theoretical results.
The sixth chapter “Synthesis and characterization of PbS micro-and
nano-crystals” presents the fabrication of flower shaped PbS crystals via
hydrothermal and microwave routes. In this chapter, PbS crystals of different
morphology and sizes have been prepared by the reaction of lead acetate and
thiourea using cetyltrimethylammonium bromide (CTAB) as surfactant through
hydrothermal and microwave methods. To study the role of reaction time in the
morphology and size, reactions have been carried out for different reaction time
in hydrothermal process. The samples were characterized by X-ray powder
diffraction (XRD), scanning electron microscope (SEM), UV-VIS-NIR
spectroscopy, Raman spectroscopy, FTIR spectroscopy and fluorescence
spectrophotometer. The results demonstrate that the reaction method and
reaction time play important role on the evolution of morphology and size of
PbS micro/nanocrystals.
The last seventh chapter “Conclusion and future scope” presents the
conclusion of the present work and some suggestions for the future work.

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List of Contents
LIST OF TABLES.................................................................................................................................IX
LIST OF FIGURES................................................................................................................................X
LIST OF ABBREVIATIONS.............................................................................................................XIV
CHAPTER 1.................................................................................................................1
INTRODUCTION.........................................................................................................1
CHAPTER 2...............................................................................................................26
THEORETICAL AND EXPERIMENTAL DETAILS...........................................26
2.1 COMPUTATIONAL DETAILS..................................................................................27
2.2 EXPERIMENTAL DETAILS.....................................................................................34
2.3 CONCLUSION.......................................................................................................57
CHAPTER 3...............................................................................................................58
STRUCTURAL PROPERTIES OF PBX (X=S, SE, TE)..........................................58
3.1 INTRODUCTION...................................................................................................59
3.2 COMPUTATIONAL DETAILS..................................................................................62
3.3 RESULTS AND DISCUSSION.................................................................................63
3.4. CONCLUSIONS....................................................................................................90
CHAPTER 4...............................................................................................................94
PRESSURE DEPENDENT ELECTRONIC AND OPTICAL PROPERTIES OF
LEAD CHALCOGENIDES........................................................................................94
4.1 INTRODUCTION...................................................................................................95
4.2 COMPUTATIONAL DETAILS..................................................................................96
4.3 RESULTS AND DISCUSSION.................................................................................97
4.4 CONCLUSIONS...................................................................................................119
CHAPTER 5.............................................................................................................123
STRUCTURAL AND ELECTRONIC PROPERTIES OF DOPED LEAD-
CHALCOGENIDES..................................................................................................123
5.1 INTRODUCTION.................................................................................................124
5.2 COMPUTATIONAL DETAILS................................................................................126
5.3 RESULTS AND DISCUSSION...............................................................................126
5.4 CONCLUSIONS...................................................................................................144
CHAPTER 6.............................................................................................................148
SYNTHESIS AND CHARACTERIZATION OF PBS MICRO- AND NANO-
CRYSTALS................................................................................................................148
6.1 INTRODUCTION..................................................................................................149
6.2 EXPERIMENTAL DETAILS...................................................................................150
6.3 RESULTS AND DISCUSSION................................................................................151
6.4 CONCLUSIONS...................................................................................................168
CHAPTER 7.............................................................................................................172
CONCLUSIONS AND FUTURE SCOPE...............................................................172
List of Publications....................................................................................................175

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List of Tables
Table 3.1 Calculated and experimental lattice parameter (a), bulk modulus
(B0), its pressure derivatives (B 0') and cohesive energy (Ecoh) for
PbS………………………………………………………………… 71
Table 3.2 Calculated and experimental lattice parameter (a), bulk modulus
(B0), its pressure derivatives (B 0') and cohesive energy (Ecoh) for
PbSe………………………………………………………………… 72
.
Table 3.3 Calculated and experimental lattice parameter (a), bulk modulus
(B0), its pressure derivatives (B 0') and cohesive energy (Ecoh) for
PbTe………………………………………………………………… 73

Table 3.4 Cohesive energy of PbS (B1 phase) at different pressures…………. 81

Table 3.5 Transition pressure (in GPa) for PbS, PbSe and PbTe……………. 89

Table 4.1 The calculated direct band gaps (in units of eV) of PbX along with
previous data……………………………………………………….. 102

Table 4.2 Dependence of the band gap on positive and negative pressures for
B1 phase of PbS…………………………………………………… 107

Table 4.3 The dielectric constant on negative and positive pressures for B1
phase of PbX……………………………………………………… 116

Table 4.4 Dependence of the dielectric constant on negative and positive


pressures for B1 phase of PbS…………………………………… 117

Table 5.1 Calculated lattice parameter (a), bulk modulus (B 0) and its pressure
derivatives (B0') for PbS1-xSex (x=0, 0.25, 0.5,0.75 and 1.0)……….. 128

Table 5.2 Calculated lattice parameter (a), bulk modulus (B 0) and its pressure
derivatives (B0') forPbS1-xTex (x=0, 0.25, 0.5,0.75 and1.0)………… 129

Table 5.3 Calculated lattice parameter (a), bulk modulus (B 0) and its pressure
derivatives (B0') for PbSe1-xTex (x=0, 0.25, 0.5, 0.75 and1.0)…… 130

Table 5.4 Energy band gap (in eV) for PbS1-xSex, PbS1-xTex and PbSe1-xTex
(x=0, 0.25, 0.5, 0.75 and1.0)……………………………………… 142

Table 6.1 FTIR band positions of pure CTAB and PbS crystals with their
assignments………………………………………………………… 165

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List of Figures
Figure 2.1 Synthesis procedure for the fabrication of PbS crystals via
hydrothermal method…………………………………………….. 36

Figure 2.2 Synthesis procedure for the fabrication of PbS crystals via
microwave method………………………………………………… 37

Figure 2.3 A schematic representation of X-ray differaction from finite number


of planes…………………………………………………... 39

Figure 2.4 Emission occurring from the sample after irradiation with electron
beam……………………………………………………………….. 42

Figure 2.5 A schematic diagram of scanning electron microscope…………… 44

Figure 2.6 A schematic diagram of UV-Vis absorption spectrophotometer … 46

Figure 2.7 A schematic representation of Rayleigh scattering, Stokes scattering


and anti-Stokes scattering………………………………. 50

Figure 2.8 A schematic diagram of FTIR spectrometer………………………. 53

Figure 2.9 A schematic diagram of Flurospectrometer……………………… 55

Figure 3.1 First-principles energy volume curves for B1, B27 and B2 phases of
PbS using the PBE correlation functional………………………. 65

Figure 3.2 First-principles energy volume curves for B1, B27 and B2 phases of
PbSe using the PBE correlation functional…………………….. 66

Figure 3.3 First-principles energy volume curves for B1, B27 and B2 phases of
PbTe using the PBE correlation functional……………………... 67

Figure 3.4 First-principles energy volume curves for B1, B27 and B2 phases of
PbS using the VBH correlation functional……………………… 68

Figure 3.5 First-principles energy volume curves for B1, B27 and B2 phases of
PbSe using the VBH correlation functional…………………….. 69

Figure 3.6 First-principles energy volume curves for B1, B27 and B2 phases of
PbTe using the VBH correlation functional…………………… 70

Figure 3.7 The pressure-volume dependency for PbS using the PBE
correlation functional……………………………………………… 75
Figure 3.8 The pressure-volume dependency for PbSe using the PBE
correlation functional……………………………………………… 76
Figure 3.9 The pressure-volume dependency for PbTe using the PBE
correlation functional……………………………………………… 77

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Figure 3.10 The pressure-volume dependency for PbS using the VBH
correlation functional……………………………………………… 78

Figure 3.11 The pressure-volume dependency for PbSe using the VBH
correlation functional……………………………………………… 79

Figure 3.12 The pressure-volume dependency for PbTe using the VBH
correlation functional……………………………………………… 80

Figure 3.13 The variation of cohesive energy of PbS (B1 phase) under pressure 82

Figure 3.14 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbS using the PBE correlation functional 83

Figure 3.15 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbSe using the PBE correlation functional 84

Figure 3.16 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbTe using the PBE correlation functional 85

Figure 3.17 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbS using theVBH correlation functional 86

Figure 3.18 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbSe using the VBH correlation
functional……………………………………………………………. 87
Figure 3.19 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbTe using the VBH correlation
functional……………………………………………………………. 88
Figure 4.1 Energy band structure B1 phase of PbS at pressure (P) = 0 GPa 99

Figure 4.2 Energy band structure B1 phase of PbSe at pressure (P) = 0 GPa 100

Figure 4.3 Energy band structure B1 phase of PbTe at pressure (P) = 0 GPa 101

Figure 4.4 Energy band structure B1 phase of PbS at pressure (P) = -2 GPa 103

Figure 4.5 Energy band structure B1 phase of PbS at pressure (P) = -1 GPa 104

Figure 4.6 Energy band structure B1 phase of PbS at pressure (P) = 1 GPa 105

Figure 4.7 Energy band structure B1 phase of PbS at pressure (P) = 2 GPa 106

Figure 4.8 Density of states of B1 phase of PbS……………………………… 108

Figure 4.9 Density of states of B1 phase of PbSe…………………………….... 109

Figure 4.10 Density of states of B1 phase of PbTe……………………………... 110

Figure 4.11 Variation of the energy band gap at (L) point with pressure for PbS 111

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Figure 4.12 Compton profile anisotropies obtained from unconvoluted
directional Compton profiles for B1phase of PbS using LCAO
method…………………………………………………………......... 112
Figure 4.13 The equal-valence-electron-density (EVED) profiles for PbS, PbSe
and PbTe…………………………………………………………… 114

Figure 4.14 The equal-valence-electron-density (EVED) profiles for PbS at


different pressures…………………………………………………... 115

Figure 4.15 Variation of the dielectric constant with pressure for PbS………… 118

Figure 5.1 Calculated lattice constants as a function of composition for (a)


PbS1-xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys…………………... 131

Figure 5.2 Calculated bulk modulus as a function of composition for (a) PbS1-
xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys………………………... 132

Figure 5.3 Energy band structure of B1 phase of PbS0.75Se0.25………………… 133

Figure 5.4 Energy band structure of B1 phase of PbS0.50Se0.50………………… 134

Figure 5.5 Energy band structure of B1 phase of PbS0.25Se0.75………………… 135

Figure 5.6 Energy band structure of B1 phase of PbS0.75Te0.25………………… 136

Figure 5.7 Energy band structure of B1 phase of PbS0.50Te0.50………………… 137

Figure 5.8 Energy band structure of B1 phase of PbS0.25Te0.75………………. 138

Figure 5.9 Energy band structure of B1 phase of PbSe 0.75Te0.25……………… 139

Figure 5.10 Energy band structure of B1 phase of PbSe 0.50Te0.50………………………….. 140

Figure 5.11 Energy band structure of B1 phase of PbSe 0.25Te0.75........................ 141

Figure 5.12 Calculated Energy band gap as a function of composition for (a)
PbS1-xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys…………………. 144

Figure 6.1 X-ray diffraction (XRD) pattern of PbS crystal obtained by


hydrothermal process (reaction time 2 h)………………………… 152

Figure 6.2 X-ray diffraction (XRD) pattern of PbS crystal obtained by


microwave process………………………………………………….. 153

Figure 6.3 SEM images of PbS crystals with a reaction time: (A) 2 h, (B) 4
h, (C) 6 h and (D) 12 h…………………………………………… 155

Figure 6.4 UV-vis absorption spectra of the PbS crystal obtained with 2 h
hydrothermal reaction time………………………………………… 157

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Figure 6.5 Plot to calculate the direct band gap of PbS sample prepared with 2
h hydrothermal reaction time……………………………………… 158

Figure 6.6 UV-vis transmittance spectra of as-prepared PbS crystals with


different reaction time………………………………………………. 160

Figure 6.7 UV-vis absorption spectra of the PbS crystal obtained with
microwave route…………………………………………………… 161

Figure 6.8 Plot to calculate the direct band gap of PbS sample prepared under
microwave irradiation……………………………………………… 162

Figure 6.9 Raman spectra of as-prepared PbS crystals with different


hydrothermal times………………………………………………… 163

Figure 6.10 FTIR spectra of CTAB and PbS crystals………………………… 164

Figure 6.11 Photo luminescence spectra of as-prepared PbS crystals via


hydrothermal reaction with reaction times: (A) 2 h , (B) 4 h, (C) 6 h
and (D) 12 h………………………………………………………… 166
Figure 6.12 Photo luminescence spectra of PbS crystal obtained by microwave
route………………………………………………………………. 167

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List of abbreviations
Numerous abbreviations are used in many parts of this thesis. For
convenience, some of them are as follows:

 APW - Augmented Plane Wave


 FP-LAPW - Full Potential Linearised APW
 LMTO - Linear Muffin Tin Orbitals
 TB-LMTO - Tight Binding LMTO
 LCAO - Linear Combination of Atomic Orbitals
 LCGO - Linear Combination of Gaussian Orbitals
 DFT - Density Functional Theory
 DFT-GGA - DFT-Generalized Gradient Approximation
 LDA - Local Density Approximation
 HF - Hartree Fock
 EPM - Empirical Pseudopotential Method
 PW-PP - Plane Wave Pseudopotential
 PBE - Perdew-Burke-Ernzerhof
 EVED - Equal Valence Electron Density
 PbX - Lead Chalcogenides
 XRD - X-ray Diffraction
 SEM - Scanning Electron Microscopy
 FTIR - Fourier Transform Infrared Spectroscopy
 NC - Nanocrystal

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Chapter 1
Introduction

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1.1 Introduction
The photovoltaic cells are very important due to their use as an alternate
source of electricity. The first generation of photovoltaic cells is based on a
single p-n junction of a crystalline-Si, exhibiting a power conversion efficiency
of 15-20%. The poor absorbing properties of the crystalline Si and its high
production cost have led to the use other various materials for photovoltaic
technologies. The binary IV-VI compounds are the oldest known
semiconducting materials used as photovoltaic materials and the most
prominent representatives such as PbS, PbSe and PbTe, have been used for
more than 100 years for electric and optoelectronic device applications. The
first reported solid state diode has been made from single crystal PbS in 1874
by Ferdinand Braun [1] and its rectifying properties have been exploited in the
early radio receivers.
The IV-VI compounds present specific electronic and transport
properties, such as narrow band gaps, low resistivities, large carrier mobilities
and positive temperature coefficients [2,3]. These properties make the IV-VI
compounds particularly applicable as electro-optical devices in the range 3-30
μm corresponding to the medium and far infrared. Due to small direct band
gap, IV-VI compounds have been widely used in many fields such as sensor,
photography, IR detector, solar cells etc. [4-15]. Because of their specific
properties and various technological applications, IV-VI semiconductors have
received a great attention of researchers.
The phase transformation in the system GeSe-GeTe has been studied by
Muir and Beato [16]. They have observed that a rhombohedral-cubic
transformation occurs at 370 ± 10°C in alloys based on the GeTe structure and
with composition in the range 0–55 mol% GeSe. The temperature and
composition dependence of lattice parameters also have been determined for
these alloys.

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Bhatia et al [17] have observed the first order transition in single crystals
GeSe near 6 GPa. They have observed the face-centered-cubic structure of
GeSe using an X-ray diffraction pattern of the quenched material. Moreover,
resistivity measurements as a function of pressure and temperature suggested
that the high-pressure phase is metallic.

The structural phase transitions in SnS and SnSe have been predicted by
Chattopadhyay et al [18] using neutron diffraction study. Later on
Chattopadhyay et al [19] have predicted the phase transition in GeS. They have
also calculated the accurate positional and thermal parameters as a function of
temperature. They have concluded that phase transitions are of second order
displacive type.

The properties of the ferroelectric IV-VI semiconductor GeTe have been


studied as a function of pressure up to 25 GPa at room temperature by Leger
and Redon [20] using powder X-ray diffraction in a diamond anvil cell.

The transverse and longitudinal optical frequencies, the dielectric


constant and the effective charges for the A4B6 type family of the
semiconducting compounds, namely, GeTe, SnTe and PbTe have been
presented by Zein et al. [21] using the density functional method with the use
of the norm-conserving "first-principles" pseudopotentials. The electronic
structure of the narrow gap IV‐VI semiconducting compounds, namely, GeTe,
SnTe and PbTe have been investigated by Ravindran and Asokamani [22] by
employing the LMTO method. They also predicted that the electronic
contribution arising from Te atom plays a dominant role in promoting
superconductivity and s and p→d electron transfer is found to be responsible
for the pressure induced superconductivity in these compounds.

Lebedev and Sluchinskaya [23] have reported the low-temperature


phase transitions in some quaternary solid solutions of IV-VI semiconductors.
They have used electrical and X-ray methods on samples PbS xSeyTe1-x-y, Pb1-
x SnxTe1-ySey and Pb1-xSnxTe1-ySy. They concluded that the phase transitions in
these solid solutions were associated with off-center S and Sn ions.

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An “in-situ” X-ray diffraction study of the GeTe under shear
deformation and nonhydrostatic pressure conditions has been performed by
Serebryanaya et al [24]. They predicted that the structure changes from NaCl to
GeS and further to CsCl types at 19.2 and 38 GPa respectively. Maclean et al
[25] have carried out high pressure angle dispersive X-ray powder diffraction
studies on IV-VI semiconductors using image plate detection. They suggested
that the high pressure intermediate phase for lead chalcogenide is monoclinic,
as opposed to previously reported orthorhombic structure.

Using a combination of high-resolution X-ray powder diffraction,


Raman scattering, and ab-initio simulation, Hsueh et al. [26] presented the
structural and vibrational properties of the prototypical layered semiconductor
GeS. They observed GeS has no structural phase transition up to at least 94
kbar.

High pressure electrical resistivity on cubic SnTe 1-xSex has been reported
by Ariponnammal et al [27]. They observed that the resistivity decreases
gradually with the increase of pressure and then reaches saturation and the
transition pressure decreases with the decrease of selenium concentration.

Structural and electrical properties of GeSe and GeTe at high pressure


have been reported by Onodera et al [28] using a combination of X-ray-
diffraction measurements, a diamond-anvil cell, and electrical-resistance
measurements by employing an octahedral-anvil press. They have revealed that
GeSe remains in the orthorhombic structure to at least 82 GPa, whereas GeTe
transforms from the rhombohedral structure to the NaCl-type phase (GeTe-II)
at 3 GPa and into another high-pressure phase (GeTe-III) at 18 GPa.

Neutron scattering experiments were performed by Raty et al [29] on the


liquid phases of a series of IV–VI compounds (GeS, GeSe, GeTe, SnS, SnSe
and SnTe). They showed that the evolution of the local order was correlated
with the conductivity measurements.

Schwarzl et al [30] investigated the plasma etching of IV-VI


nanostructures using a CH4/H2 gas mixture. They predicted that etch rate
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decreases with the energy band gap. Furthermore, they also investigated the IV-
VI quantum wires with vertical side walls by a combination of laser holography
and CH4/H2/Ar plasma etching.

The three-dimensional ordering of the PbSe dots in a trigonal lattice


with a fcc-like ABCABC vertical stacking sequence have been showed by
Springholz et al [31] using self-organization of PbSe islands in epitaxial
PbSe/Pb1−xEuxTe superlattices. Using X-ray diffraction they predicted that
reciprocal space maps, the interlayer correlation direction of the PbSe dots
were to be inclined by 400 with respect to the [111] surface normal. Peak
profile measurements of ordered regions showed coherence length of order of
300±100 nm in the lateral, and of 530±50 nm in the vertical direction.

The structure and dynamics of semiconducting liquid GeSe using


ab-initio molecular-dynamics simulations have been investigated by Raty et al
[32]. They showed that the Peierls distortion reenters GeSe in the melt phase.
They also examined the distance histograms and concluded that there is one
Ge-Ge defective bond in GeSe3 unit. Further, the calculated viscosity and
electrical conductivity were in good agreement with the experiment.

The structural and optical characterizations of colloidal PbSe


nanocrystals have been presented by Du et al [33]. They have concluded that
lowest-energy exciton transitions in these structures, with diameters between 3
and 8 nm, occur at wavelengths between 1.0 and 1.85 μm. Moreover,
unexpectedly long ( 300 ns) luminescence lifetimes have also been observed.

The structural properties, electronic energy band structure and some


optical properties of SnTe and GeTe have been calculated by C.M.I. Okoye
[34] using the FP-LAPW method within LDA and GGA schemes. He has also
considered the effects of spin-orbit interactions. The variations of the band gaps
with temperature as well as the dielectric functions have also been discussed.

Khokhlov and Volkov [35] have investigated the Fermi level pinning
and long-term relaxation effects in doped IV-VI narrow-gap semiconductors.
They predicted that the doping of PbTe-based alloys with some of the group III
xix | P a g e
impurities lead to an appearance of unusual impurity states in these narrow-gap
IV-VI semiconductors. Structural and optical properties of CdSe, CdTe and
CdSeTe nanoparticles dispersed in SiO2 films have been investigated by Dayal
et al [36]. They have grown CdSexTe1-x nanoparticles (with different
stoichiometry ratio x) by magnetron sputtering technique followed by thermal
annealing. Using the GAXRD, XPS, TEM and spectroscopic ellipsometry
techniques, the effect of thermal annealing conditions on the structural,
compositional, optical and electronic properties of nanoparticles have also been
studied. Initial observations from the ellipsometry measurements carried out on
some of these nanoparticle films have shown a blue shift of absorption edge.

The structural behavior of SnS under high-pressure were investigated by


Ehm et al [37] using angular dispersive synchrotron powder diffraction up to
38.5 GPa. A structural phase transition from orthorhombic to monoclinic was
observed to be at 18.15 GPa. The improper ferro-elastic transitions were also
observed and accompanied by a large volume discontinuity of about 9.1%.

The variation of the EPR (electron paramagnetic resonance) and NMR


(nuclear magnetic resonance) spectra of active centers generated by disorder in
the IV-VI semiconductor matrices have been presented by Zayachuk et al [38].
They have studied both undoped and doped with Gd impurity powder samples
of different grain sizes, made from Pb(1-x)Sn(x)Te crystals. They have found
that grinding of the single crystals into powders leads to an additional
component line appearing in the NMR spectra and also significant increase in
the intensity of EPR spectra. Both spectra undergo modifications due to
isothermal annealing.

M. Duranduurdu [39] studied the pressure-induced phase transition in


GeS using a molecular dynamics within DFT. He predicted a slow phase
transition to a Cmcm structure with the application of hydrostatic pressure. He
also reported the metallization of GeS prior to transforming into the Cmcm
phase. Mn 3d electronic structure in IV–VI ferromagnetic semiconductor Ge1-
x MnxTe (x = 0.32) were investigated by Sato et al [40] by using soft X-ray

xx | P a g e
magnetic circular dichroism (XMCD) measurements. The parameters such as
the p-d hybridization and p-d exchange constant N0β were also estimated.

Using the first-principle density functional total energy calcilations by


the TB–LMTO approach, Rajagopalan et al [41] reported the structural
properties of SnS under pressure. They found that SnS undergoes a structural
phase transition from orthorhombic type to monoclinic type structure at about
17 GPa. Further, they also investigated the band structures of SnS and reported
that it has a narrow indirect gap. They also observed that with increase in
pressure, direct gap decreases at high rate as compared to the indirect gap. The
effect of pressure on ferroelectric GeTe was investigated by Ciucivara et al [42]
using density functional calculations. They compared both LDA and GGA
calculations. They reported that except for the energy gap, the GGA results
were slightly better than the LDA.

Edwards et al [43] investigated the electronic structure and formation


energies of the vacancy and antisite defects in GeTe. They showed that nature
of free-carrier transport in crystalline GeTe can be determined by intrinsic
defects. The physical principles of operation of the photodetecting devices
based on the group III-doped IV-VI compounds were reviewed by Khokhlov
and Dmitry [44]. They also explained the possibilities of fast quenching of the
photoresponse, construction of a focal-plane array, a new readout technique etc.
Furthermore, they demonstrated the importance of the infrared photodetecting
systems based on these materials as compared to the modern photodetectors.

Victor I. Klimov [45] presented the review on mechanisms for


photogeneration and recombination of multiexcitons in semiconductor
nanocrystals. He particularly focused on the fine structure of the band-edge
optical transitions and its effect on temperature-dependent single-exciton
recombination dynamics. Along with this, he also discussed the Auger
recombination of multiexcitons in nanocrystals.

A comparative study of photodetector performance for nano- and micro-


crystalline PbS thin layers have been presented by Iordache et al [46]. They

xxi | P a g e
have used chemical bath deposition method to prepare the films. The synthesis
of SnTe nanocrystals have been demonstrated by Kovalenko et al [47] by the
reaction of bis [bis(trimethylsilyl)amino] tin(II) with trioctylphosphine telluride
in oleylamine. They observed that SnTe nanocrystals are single-crystalline
particles with a cubic B1 structure. They reported that SnTe nanocrystals
exhibit size-tunable band gap energies of 0.38−0.8 eV.

The magnetic and transport behaviours of Ge1−xMnxTe thin films have


been studied by Chen et al [48]. They have grown these films by solid-source
molecular-beam epitaxy. They have explained the ferromagnetism in
Ge0.02Mn0.98Te on the basis of the Ruderman-Kittel-Kasuya-Yoshida interaction
and clustering effect.

Microstructural properties of GeTe thin films were investigated by Kim


et al [49] by using in-situ heating method within a high voltage electron
microscopy (HVEM). They observed that the fcc-GeTe transforms into
orthorhombic structure and the crystallization behavior of GeTe orthorhombic
structure in the HVEM is different from thermal crystallization. M. Khodr [50]
presented the effects of non parabolic bands on nanostructure laser devices. He
developed a theoretical model based on the energy dependent effective mass to
study this effect on several lead salt (IV-VI) laser nanostructures in the infrared
region.

Colloidal hybrid nanoparticles of II–VI and IV–VI groups on top of


FePt particles were synthesized by Zanella et al [51]. They reported a
significant fluorescence quenching of the semiconductor because of the
presence of FePt (iron-platinum) particle.

Dantas et al [52] investigated the electronic band-edges of PbX and SnX


(where X = S, Se and Te) by the FP-LAPW method and the local density
approximation (LDA). They observed that all these compounds have similar
electronic structures and density-of-states, but there are differences in the
symmetry of the band-edge states at and near the Brillouin zone L-point.

xxii | P a g e
SnSe, SnSe2, and Sn2Se3 alloys have been studied by Chung et al [53] in
order to explore their suitability as new phase change alloys for electronic
memory applications. They also determined the temperature dependence of the
structural and electrical properties of these alloys and compared with that of
GeTe. The microstructures of these alloys have been also investigated by
atomic force microscopy measurements. X-ray reflection measurements
revealed density increases of 5.0%, 17.0% and 9.1% upon crystallization for
the different alloys.

The synthesis and characterization of monodisperse SnS nanocrystals


have been presented by Hickey et al [54]. They also demonstrated the shape
control by varying the ratio of ligands present in the reaction mixture. Gao and
Daw [55] have studied systematically the band structure of PbTe and SnTe
alloys using first-principles calculations within GGA. By taking into account
local disorder, they showed that the calculated dependence of band gap on
composition is in good agreement with experimental results.

The dynamical, dielectric, and elastic properties of GeTe in its low-


temperature rhombohedral phase have been investigated by Shaltaf et al [56]
using first-principles DFT. They have reported the electronic energy bands,
phonon-dispersion curves, electronic and low-frequency dielectric tensors,
infrared reflectivity, Born effective charges, and elastic and piezoelectric
tensors.

A study of electron momentum density distribution in SnS by means of


Compton profiles has investigated by Sharma et al [57]. The measurement on
polycrystalline sample of SnS has been performed by employing 59.54 keV
gamma-rays emanating from an Am 241 radioisotope. They have performed
calculations on the basis of DFT based ab-initio LCAO method embodied in
the CRYSTAL program.

With the use of one-step vapour transport process, self assembly of


highly aligned GeTe nanowires epitaxially growth on octahedral GeTe
microcrystals have reported by Chung et al [58]. The growth of doped PbTe

xxiii | P a g e
epitaxial film has reported by Koenig et al [59]. They measured thermal
conductivity of film with the time-domain thermal reflectance method. The
structure of film has investigated by X-ray diffraction (XRD) measurements.

The band gap location and core spectra of orthorhombic IV–VI


compounds SnS and SnSe have been investigated by Makinistian and Albanesi
[60] using an ab-initio DFT method. They have showed that the spin–orbit
interaction produces slight splittings of bands in both compounds, especially in
the conduction band. Furthermore, several aspects of the crystals anisotropy
have also been explained on the basis of hybridized band structure, the density
of states (DOS) and the optical spectra (complex dielectric function and
absorption coefficient).

Volykhov, et al [61] calculated the phase diagrams of all the


pseudoternary systems formed by the Group 14 chalcogenides: (Ge, Sn, Pb) Te,
Pb(S, Se, Te), and Sn(S, Se, Te). They observed that systems have small
negative ternary interaction parameters, which decreases in the order β-(Ge, Sn,
Pb)Te < β-Pb(S, Se, Te) < δ-Sn(S, Se, Te). The new strategies for band gap and
electronic wave function engineering to control the location of charge carriers
have been discussed by Smith and Nie [62].

Kuo and Huang [63] reported the different synthetic methods for the
growth of Cu2O nanocrystals with morphological control. They revealed that
Cu2O nanocrystals with cubic, cuboctahedral, truncated octahedral, octahedral
and multipod structures have been prepared by wet chemical, electrodeposition,
and solvothermal synthesis methods. They examined surface properties of
Cu2O nano- and micro crystals with sharp faces. They concluded that the {111}
faces interact well with negatively charged molecules whereas {100} faces are
less sensitive to molecular charges.

Structural phase transitions of GeTe have been predicted by Do et al


[64] by the means of ab-initio pseudopotential density functional method. They
have investigated transition pathways and pressures for NaCl to CsCl structures
by considering three different paths, namely, the Watanabe, Tolédano, and

xxiv | P a g e
modified Buerger. Structural and electronic properties of the phases are also
presented near the transition pressures. They showed that GeTe exhibits very
complex transition behaviours at intermediate pressures around 20 GPa.

Phase transitions in GeTe/SnSe and Ge2Se3/SnTe have been investigated


by Devasia [65] using time resolved X-ray diffraction. They observed that
GeTe exhibited a structural transition from rhombohedral to the cubic phase at
300°C. Amorphous Ge2Se3 also found to crystallize in orthorhombic GeSe and
monoclinic GeSe2 at 300°C. They concluded that inclusion of Sn layer offers a
means to tailor phase transition in Ge-chalcogenide thin films for phase change
memory applications.

The platelet-like hydrazine–cadmium tellurite hybrid microcrystals have


been synthesized by a Yao et al [66] using solvothermal reaction of cadmium
chloride, sodium tellurite, and hydrazine hydrate in a mixed solvent which
contains n-propylamine and deionized water. The resulting microcrystals have
characterized by XRD, element analysis, TGA (thermogravimetic analysis) and
XPS. They have also studied Brunauer–Emmett–Teller (BET) analysis and
optical properties of this porous cadmium telluride and suggested that the
synthesized hybrid microcrystals can be used in sensor devices or as templates
in the synthesis process of other porous materials.

Hoang et al [67] presented the first-principles studies of the energy


bands associated with various monovalent (Na, K, and Ag) and trivalent (Sb
and Bi) impurities and impurity clusters in PbTe, SnTe, and GeTe using
supercell models. Monovalent and trivalent impurity atoms are found to tend to
come close to one another and form impurity-rich clusters and the electronic
structure of the host materials is strongly perturbed by the impurities.

The synthesis of Zn1–xSnxS (x = 0, 0.1, 0.2, 0.3) nanoparticles and their


photoluminescence properties have been reported by Pawar et al [68]. They
have synthesized these particles by using thiourea as a capping agent. They
calculated the particle size of Zn 1–xSnxS nanoparticles using XRD, which is

xxv | P a g e
found in the range of 12-24.5 nm. They also reported that, the addition of Sn 2+
ions causes the change in UV and PL spectra of ZnS nanoparticles.

The stability of SnS at high pressure has been studied by Alptekin and
Durandurdu [69] using a constant pressure ab-initio technique. They reported a
pressure-induced phase transformation from the Pnma structure to a Cmcm
structure. They also observed that Cmcm phase is still a layered structure,
consisting of rocksalt-like bilayers, similar to that formed at high temperatures.
The phase change has also reported by total energy calculations.

Using the LCAO method, the electronic structure and ground state
properties of the IV-VI semiconductor, SnTe have been investigated by Sharma
et al [70]. They have used the calculated Compton profiles to discuss the
electronic properties of SnTe. They also examined the nature of bonding and
concluded that SnTe is more ionic as compared to GeTe.

Using an angle-resolved photoemission spectroscopy, the electronic


structure of SnTe has been studied by Littlewood et al [71]. They compared
their experimental results with ab-initio band structure calculations as well as a
simplified tight-binding model of the p-bands. The structural behavior of SnSe
under the hydrostatic pressure using a constant pressure ab-initio technique has
been investigated by S. Alptekin [72]. He found that SnSe undergoes a
structural second order phase transition from the orthorhombic (Pnma)
structure to orthorhombic (Cmcm) structure at 7 GPa. He also studied the
behavior of SnSe under uniaxial stress. Antunez et al [73] made recent efforts
towards achieving synthetic control over nanocrystal size and morphology of
the non-lead containing IV–VI monochalcogenides (i.e., SnS, SnSe, SnTe, GeS
and GeSe) and their applications in the field of photovoltaic devices.

The structure, composition and galvanomagnetic properties of the single


crystal Pb1-x-ySnxVyTe, Pb1-yTiyTe and Pb1-yScyTe with the variation of the alloy
composition (x ≤ 0.20 and y ≤ 0.025) have been studied by Skipetrov et al [74].
Wang et al [75] have investigated the structural, energy stability, and magnetic
properties of the diluted magnetic semiconductors Sn 1-xGdxTe (x=3.125 %, 6.25

xxvi | P a g e
% and 12.5 %) with the use of DFT. They calculated the lattice parameters of
the Sn1-xGdxTe compounds at zero pressure and zero temperature, which are in
very good agreement with the experimental data. They also investigated the
energy stability of different configurations, which shows that Gd atoms prefer
to occupy the nearest neighbor positions to the next nearest.

Brusilovski et al [76] have synthesised PbSexS1–x and PbSe/PbSexS1–x


nanorods with a diameter between 2 and 4.5 nm and length of 10 to 38 nm.
Structural and optical characterizations of the samples were also reported. They
concluded that the energy band gap of the nanorods shows a prominent
variation with the change in diameter and composition. Dziawa et al [77]
reported that the narrow-gap semiconductor Pb 1−xSnxSe (with x= 0.23) is a TCI
(topological crystalline insulators), a class of topological insulators in which
crystalline symmetry replaces the role of time-reversal symmetry in ensuring
topological protection. The result of Temperature-dependent angle-resolved
photoelectron spectroscopy demonstrates that the material undergoes a
temperature-driven topological phase transition from a trivial insulator to a
TCI. The possibility of a mirror symmetry-protected topological crystalline
insulator phase in the Pb1-xSnxTe class of materials has been experimentally
investigated by Xu et al [78].
The structural, electronic and optical properties of Be-doped CdS, CdSe
and CdTe compounds with the dopant concentration x in the range 0≤x≤1, have
been presented by Noor et al [79]. They have used FP-LAPW plus local
orbitals method within DFT. They have investigated the density of states
curves, charge density maps and dielectric function. Structural and chemical
factors that affect the band-gap bowing of these semiconductor alloys are also
discussed. Etgar et al [80] have reported solid state PbS quantum dots
(QDs)/TiO2 heterojunction solar cells. They have deposited PbS QDs on a 500
nm thick mesoscopic TiO2 films with the use of layer-by-layer deposition. They
have reported that the PbS QDs act as photosensitizers and hole conductors
simultaneously in this solar cells. A short circuit photocurrent (J sc) of 13.04

xxvii | P a g e
mA/cm2, an open circuit photovoltage (Voc) of 0.55 V and a fill factor (FF) of
0.49 can be produced by the PbS QDs/TiO 2 device. Along with this, they also
investigated the electric process of this device by transient photocurrent and
photovoltage measurements as well as impedance spectroscopy in the dark and
under illumination.
With the use of a CMOS-compatible process, coupling of the excitonic
photon emission from photo-excited PbSe colloidal quantum dots (QDs) into
an optical circuit has presented by Foell et al [81]. Benehkohal et al [82] have
reported the development of quantum dot sensitized solar cells (QDSCs) using
colloidal PbS and PbSe quantum dots (QDs) and polysulfide electrolyte for
high photocurrents. The photoluminescence spectra of colloidal core–shell
PbSe/PbS QDs with type II alignments in the valence band have been
investigated theoretically by Aeberhard et al [83]. Etgar et al [84] have
employed quasi type-II PbSe/PbS quantum dots in solid state high efficiency
QD/TiO2 hetrojunction solar cells.
Ardakani et al [85] reported the synthesis of PbS nanocrystals in a non-
coordinating solvent, 1-octadecene, using oleic acid (OA) as the ligand. They
presented the influence of the thickness of colloidal lead sulfide (PbS)
nanocrystals (active layer) to the photovoltaic performance of colloidal
quantum dot solar cells. The device with 50 nm of thickness of active layer has
found to be highly efficient with efficiency (η) of 0.667 compared to the device
with low thickness of active layer. Piliego et al [86] investigated the impact of
post-synthetic treatments of nanocrystals (NCs) on the performance of
Schottky solar cells. The active PbS nanocrystal layer can be sandwiched
directly between two electrodes in Schottky solar cells. They found that
optimized processing conditions can lead to high current density. Hence overall
efficiency can be increased. The efficiency of their PbS nanocrystal Schottky
solar-cell is 5.2%.
Using diffuse reflectance infrared Fourier transform spectroscopy,
optical absorption edge measurements on I doped PbTe have been performed
by Gibbs et al [87]. They reported that the optical gap increases on the order of

xxviii | P a g e
0.1 eV for doping levels ranging from 3× 1018 to 2 × 1020 cm-3. They estimated
chemical potential from transport measurements like Hall effect and Seebeck
coefficient with the use of a single band mode. Preetha et al [88] presented the
growth of thin films of PbS on soda lime glass substrate by successive ionic
layer adsorption and reaction (SILAR) method. They have used lead acetate,
lead chloride, lead nitrate and lead sulphate as cationic precursors and
thioacetamide as sulphur source. Samples have characterized by means of XRD
and SEM. They presented that the size of the crystallites affects the structural,
morphological and optical properties of PbS thin films.
Douri et al [89] have prepared CdS nanostructures by sol-gel coating
method with different thiourea concentration. They presented the effect of
thiourea concentration on CdS nanostructures. CdS nanostructures have been
characterized with X-ray diffraction, optical transmittance, atomic force
microscopy and photoluminescence spectroscopy. They have calculated
refractive index and dielectric constant of these nanostructures. Merino et al
[90] prepared nanocrystalline PbS thin films by chemical bath deposition
(CBD) at 40 ± 2°C on glass substrates. They have modified the structural and
optical properties of PbS thin film by in-situ doping of Hg. The morphological
changes of the layers have been studied with the use of SEM and the X-rays
spectra.
With the use of FP-LAPW method, structural, electronic and optical
properties of CdSxSe1-x at various compositions (0 ≤ x ≤ 1) have been
investigated by Khan et al [91]. They observed a structural phase transition of
CdSxSe1-x from zinc-blende to wurtzite with increasing sulpher concentration.
They have reported the phase transition and structural parameters like ground
state energies, lattice constants and bulk moduli have been reported and found
in agreement with the experimental results. Wong et al [92] have reported the
structural and electronic properties of the ferromagnetic (FM) and
antiferromagnetic (AF) ordering in the PbS-based ternary alloys Pb1−xEuxS
(0 ≤ x ≤ 1) by using first-principles full-potential method. They concluded that

xxix | P a g e
the Pb1−xEuxS alloys have a direct band gap and in these alloys, AF is the
preferred magnetic order.
The highest open-circuit voltages (Voc) for colloidal QD based solar
cells under one sun illumination have reported by Yoon et al [93]. They have
reported Voc value 692 ± 7 mV for 1.4 eV PbS QDs. They concluded that the
Voc can be improved to greater than 1 V by using smaller QDs in QD solar
cells. Jain et al [94] have presented the synthesis of PbS nanospheres via the
template method. They have reported the structure, morphology and optical
properties of the hollow PbS nanospheres. Koh et al [95] have achieved
persistent n-type doping in PbSe and PbS NCs via charge-transfer from the
relatively mild reducing agent cobaltocene.
Gupta et al [96] investigated the high pressure phase transition, elastic
and electronic properties of lead-chalcogenides including the less known lead
polonium by performing ab-initio calculations using fully relativistic pseudo-
potential approach. They reported that PbS, PbSe, PbTe and PbPo undergo a
first-order phase transition from rock-salt to CsCl structure at 19.4, 15.5, 11.5
and 7.3 GPa, respectively. A facile and low-cost phosphine-free method for
synthesizing spherical PbSxSe1−x NCs has been reported by Goan et al [97].
Zeng et al [98] have studied the geometrical and electronic structures of the
PbSe clusters within the DFT framework including spin-orbital (SO) coupling.
They concluded that that SO coupling does not change the relative stability of
the clusters but reduces their binding energy significantly.
Saini et al [99] have reported the electronic and magnetic properties of
Cr-doped Cd-Chalcogenides, Cd1−xCrxZ (Z= S, Se and Te) for dopant
concentration, x=0.25 and 0.125, using FP-LAPW method within GGA as
exchange–correlation (XC) potential. Hendon et al [100] have calculated the
thermodynamic and electronic properties of a family of M(C X) metal-organic
systems (M = Mg, Ca, Zn, Cd, Hg, Ge, Sn, Pb; X = O, S, Se, Te). They found
that their electronic and enthalpic properties can be tuned through
compositional control.

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Chapter 2

Theoretical and experimental details

xxxix | P a g e
This chapter contains two main parts: 2.1 Computational details and 2.2
Experimental details. Theoretical and experimental details are discussed in
section 2.1 and 2.2 consequently.

xl | P a g e
2.1 Computational details
2.1.1 Introduction
The theoretical study of structural, optical and electronics properties of lead-
chalcogenides PbX (X=S, Se and Te) were performed with CRYSTAL [1] code
which is based on ab-initio calculations of ground state energy, energy gradient,
electronic wave functions and properties of periodic systems. The researchers
of the Theoretical Chemistry group in Torino (Italy) and the Computational
materials sciences group in CLRC (Daresbury, UK) developed this code. With
the use of this package, ab-initio calculations of ground state properties of the
periodic systems in 3D (crystals), 2D (slabs), 1D (polymers) and 0D
(molecules) can be performed.
At the present time, electronic band structure calculations are being widely
used by theoretician and experimentalists to explore the electronic, optical and
magnetic properties, etc. of various compounds. There are two fundamental
schemes to study the structural, electronic and other important properties of
compounds: Hartree-Fock (HF) approximation and density functional theory
(DFT). For the sake of completion, a brief discussion of HF and DF theory are
described below.
2.1.2 Hartree- Fock (HF) theory
HF theory was discovered by D.R.Hartree in 1927. It is an iterative
method to find out the ground state energy and the wave function. In this
theory, the whole information of system is confined in the wave function of that
system. This theory is mainly used in Quantum Mechanics and Atomic and
molecular Physics to solve the many body problems.
HF theory is an ab-initio method for solving the many-body Schrödinger
equation i.e.
Hψ i (1, 2, ... N)  E i ψ i (1, 2, ... N) (2.1)
where H is the Hamiltonian of a quantum mechanical system composed of N
particles, ψ i is its ith wave-function and E i is the energy eigen value of the i th
state. The coordinates (1, 2, ... N) are particle coordinates and are usually
associated with a spin and a position coordinate.

xli | P a g e
For electronic systems the Hamiltonian (within non-relativistic
approximations) for an N-electron system is:

1 N 2 N
1 N
H  
2 i 1
i  
i  j ri  r j
  (ri )
i 1
(2.2)

where the first, second and third terms of right hand side represent the electron
kinetic energy, the electron-electron Coulomb interactions and the coulomb
potential generated by the nuclei. It is assumed that the nuclei are effectively
stationary with respect to electron motion (Born-Oppenheimer approximation).
The HF method attempts to transform the full N-body equation into N single-
body equations. One can determine the ground state of the Hamiltonian, H,
quantum mechanically by means of the variational principle for the normalised
eigen function  (1, 2, ... N) :
 H    ...   * (1, 2, ..., N) H  (1, 2, ..., N) d r1 d r2 ... d rN  minimum  E 0
s1 s2 sN

(2.3)
where, s i is the spin direction of the ith electron.
2.1.3 Density Functional Theory (DFT)
DFT is a quantum mechanical modeling method which is widely used to
investigate ground state properties of different materials. With the use of DFT ,
the properties of many-electron system can be determined by using functional
i.e. functions of another function, which is spatially dependent electron density
in the case of DFT. It is the most versatile method of electronic structure
calculations in condensed matter physics.
The concept of DFT is based on two remarkable Hohenberg- Kohn
theorems.
The first Hohenberg-Kohn theorem [2] states that the ground state energy
of a system of electrons is a unique functional of ground state density:
EGS  E[nGS ] (2.4)

Not only ground state energy of a system but all properties of the system
including excited state properties are exact functionals of the ground state
xlii | P a g e
density because there is one-to-one mapping between the ground state density
and the external potential. If the ground state density is known then, in principle,
the external potential is known and the external potential can solve the many-
electron Schrodinger equation, hence everything about the system can be known.
The internal electronic energy F, of a system in its ground state can be
expressed as
F  E  Vext (2.5)
where Vext is the external potential energy, given by
Vext  �
n(r )vext (r )dr (2.6)
Since E and Vext are functions of the density, it follows that F is also functional of
the density. Hence it can be written
E( v , N ) [ n ]  F [ n ]  �
n0 (r )v(r )dr (2.7)
The second Hohenberg-Kohn theorem states that if N interacting electrons move

in an external potential vext (r ) , the ground state electron density no (r ) minimizes


the functional
E [ n]  F [ n]  �
n(r )v (r )dr (2.8)
where, F is a universal functional of n and the minimum value of the functional
E is E0 (the exact ground state electronic energy).
Kohn and Sham [3] derived few differential equations enabling the
ground state density n0 (r ) to be determined. Kohn-Sham equation is defined by
a local effective external potential in which the non-interacting particles move,

known as Kohn-Sham potential. This potential is denoted by veff (r). The


Hamiltonian of the non-interacting system is given as:
N
 h2 N
Hˆ s  � �i2  �veff (ri ) (2.9)
i 2m i

The wave function describing this system is a Slater determinant constructed


from a set of orbitals that are the lowest energy solutions to
� h2 2 �
fi (r )  e ifi ( r )
�2m �i  veff (r ) � (2.10)
� �

xliii | P a g e
This equation is typically representation of the Kohn-Sham equations. Here, e i is

the orbital energy of the corresponding Kohn-Sham orbitals, fi , and the electron
density distribution is given by:
N
n(r )  �fi (r )
2
(2.11)
i 1

The total energy of a system is expressed as a functional of the charge density as


E [ n ]  Ts [n]  �
n(r)vext (r)dr  VH [ n ]  Exc [n] (2.12)

where, Ts [n] is the Kohn-Sham kinetic energy which can be expressed in terms
of the Kohn-Sham orbitals as
N
�h2 �
Ts [n]  �� drfi* (r ) � �2 �
fi (r ) (2.13)
i 1 �2m �
vext (r ) is the external potential acting on interacting system, VH is the Hartee

energy which is expressed as


e2 n(r ) n(r ')
VH  ��dr dr ' (2.14)
2 r  r'

and Exc [n] is the exchange-correlation energy. The Kohn-Sham equations can be
originated by varying the total energy expression with respect to a set of orbitals
to obtain the Kohn-Sham potential as
n(r� )
veff (r )  vext (r )  � dr '  vxc (r ) (2.15)
r - r�

With the exchange-correlation potential is defined as


d Exc [ n ]
vxc (r )  (2.16)
d n(r )
The above equations provide a theoretically exact method for finding the ground
state energy of an interacting system provided that exchange-correlation energy
Exc is known.

2.1.4 Exchange-correlation potential

xliv | P a g e
The investigation of accurate and suitable exchange-correlation energy
E xc is the greatest challenge in the density functional theory. The
approximations can be divided into two classes.
Local Density Approximation (LDA)
Local Density Approximation (LDA) is that class of approximations to
the exchange-correlation energy functional that depends only on the value of the
electronic density at each point in space. Local approximations are derived from
the homogeneous electron gas (HEG) model. In the local density approximation,
the exchange and correlation energy is given
n(r )e xc (n)dr
ExcLDA [n]  � (2.17)

where, n is the electronic density, e xc is the exchange and correlation energy per
particle. The function e xc can be divided into two parts as
e xc (n)  e x (n)  e c ( n) (2.18)

where e x (n) and e c (n) are exchange and correlation contributions respectively.
Initially, the exchange contribution was given by the Dirac exchange energy
functional [4]:
1/ 3
3 �3 �
e x (n)   � � n(r)1/ 3 (2.19)
4 �p �

Accurate values of correlation part e () are available in the literature [5,6].
c

The von Barth-Hedin [vBH] is the most popular LDA scheme in the solid state
applications.
Generalised Gradient Approximation (GGA)
LDA is suitable only for those systems which have uniform electron
density distribution. LDA does not include the effects of inhomogeneity of the
electron density distribution. The exchange- correlation energy for the systems,
which have non-uniform charge densities, can be derived by GGA. Hence, in
GGA, an improvement is made by considering the dependence of exchange
correlation functional on the electron density and on the gradient of the electron
density distribution at the point of consideration. Mathematically, the

xlv | P a g e
exchange-correlation energy, in the generalized gradient approximation, can be
written as
ExcGGA  Exc [ n(r), �n(r) ] (2.20)
There are several proposed GGA schemes. One of these is due to Perdew and
Wang [7]. The hybrid functional like B3PW and B3LYP can be computed using
the Becke exchange [8] combined with the Perdew-Wang GGA correlation
scheme.
2.1.5 Ground state properties
Various ground state properties can be calculated using the CRYSTAL code as
follows:
Structural parameters
In order to calculate the structural parameters like lattice parameter (a), bulk
modulus (B0) and its pressure derivatives (B0'), the total energy versus volume
dependency for different crystal structures is to be determined. Subsequently,
these values can be fitted to the Birch Murnaghan equation of state [9,10].

9V B ��V 2/3 �3
� 2/3
V0 �
2
�� � 2/3 �
V0 � �
�� 0 � � � (2.21)
E ( V )  E0  0 0 �V �  1�B0  �
��
'
�V �  1��6  4� � � �
16 �� �
� � � �
� �� �V � � �

where, E0 is minimum energy per formula unit in the equilibrium, V 0 is
corresponding volume, B0 is the bulk modulus, and B0' is pressure derivative of
the bulk modulus.
The pressure versus volume data for the compounds can be calculated from the
third order Birch-Murnaghan [9,10] isothermal equation of state relating
pressure and volume as follows:
� V0 � �� �V0 � � �
7/3 5/3 2/3
3B0 �V0 � � � 3 ' � �
P(V ) 
2 �V � �V � �� 4 ( 0
�  1  B  4 ) �V �  1�
� � (2.22)
� � � � ��
� � � �
� �
To determine the transition pressure, the Gibbs free energy (G = E o + PV
- TS) is used. At zero temperature the thermodynamically stable phase is that
one which has lowest enthalpy, H = E + PV, at a given pressure. The variation
in the enthalpy (H) of compound with pressure (P) is to be plotted in stable and

xlvi | P a g e
other phases. When the enthalpy of the lower pressure phase coincides with
that of other phase, the transformation from one phase to another phase occurs.
Optical properties
The dielectric constant of a compound can be determined by the finite
field approach which is embodied in CRYSTAL06 code. To evaluate the
dielectric constants for compounds, following steps are to be followed:
a) Evaluation of the perturbed total energy (TE) and the electron
density of the system by running the calculations (keyword FIELD).
b) Determination of dielectric tensor element by running the properties
calculation (keyword DIEL).
Electronic properties
To study the electronic properties of different compounds, the
calculations of band structure and densities of states (DOS) of compounds are
to be made through CRYSTAL06 code. The keyword BAND is used to
compute the band structures. For the band structure, the input requires:
a) The path of the Brillouin zone in reciprocal space.
b) Number and range of energy bands.
c) Number of k-points in the Brillouin zone.
To calculate the DOS, the keyword NEWK is used. For DOS, the input
requires:
a) The energy range of DOS
b) The degree of polynomials
Electron momentum density
The valence electron momentum density is an important ground state
property. In the independent particle model, the momentum density n(p) is
given by [11, 12]
2
n ( p )  ��y i ( r ) exp(ip.r ) dr (2.23)
i

where n(p) is the three dimensional momentum density and ψ(r) represents the
electron wave function. The summation is all over the occupied states. The
Compton profile can be derived from the ground state momentum density n(p)
as

xlvii | P a g e
� �
J ( p z )  � �n ( p ) dp x dp y (2.24)
� �

The spherically averaged Compton profile is determined by the


averaged momentum density as
�
J ( p z )  2p ��n ( p) �
pdp (2.25)
pz

To evaluate the electron momentum density, the keyword PROF is used. The
input requires:
a) The momentum range along z-axis.
b) Symmetry directions like [100], [110], [111], [001] etc.

2.2 Experimental details


2.2.1 Introduction
The nanomaterials have attracted enormous attention due to their size-
dependent unique mechanical, physical and chemical properties. Earlier the
efforts were limited to produce nanomaterials in uniform sizes but with rising
techniques, which provides better control over the reaction parameters, it is
possible to synthesis them not only in uniform sizes but in uniform shapes also.
This chapter presents hydrothermal and microwave route to produce the PbS
micro- and nano-crystals of different morphologies. For the sake of completion,
a brief description of characterization techniques used for studying the different
properties of PbS crystals are described here.
2.2.2 Synthesis procedures
PbS crystals were synthesized with hydrothermal and microwave
methods. To synthesis PbS crystals via hydrothermal process, 0.036 mol lead
acetate, 0.142 mol thiourea and 8.57 mmol CTAB were dissolved into 40 mL,
20 mL and 20 mL deionized water, respectively. Then thiourea was added with
lead acetate drop wise under constant stirring condition at room temperature
followed by CTAB solution.

xlviii | P a g e
The mixture was transferred to 100 mL Teflon lined stainless steel auto
clave. After sealing, the auto clave was maintained to 180°C for different
times (2 h, 4 h, 6 h and 12 h) and cooled to room temperature naturally.
In the microwave method, the mixture was transferred to microwave
vessel and irradiated under microwave radiations for 5 min.
The post reaction treatment procedure is the same for both methods.
After cooling to room temperature, the precipitates were filtered off and
washed with distilled water and absolute ethanol. After drying in air at 60°C
for 6 h, the final products were collected for characterizations.
A schematic diagram for the synthesis of PbS crystals via hydrothermal
and microwave route are shown in Figure 2.1 and 2.2 respectively.
2.2.3 Characterization Techniques
In this work characterization of PbS crystals was carried out using
various techniques such as by X-ray powder diffraction (XRD), Scanning
electron microscopy (SEM), UV-VIS-NIR spectroscopy, Raman spectroscopy,
Fluorescence Spectroscopy and FTIR spectroscopy. A brief description of
these techniques, their principle and working, are given in following section.
X-ray Diffraction (XRD)
X-rays are electromagnetic radiation with wavelengths in the range 0.5-
2.5Ǻ. Since this is of the equal order of magnitude as the interatomic distances
in solids, X-rays are frequently used to study the internal (crystalline) structure
of materials.
X-rays are produced when electrically charged particles of sufficient
energy are decelerated. In an X-ray tube, the high voltage maintained across the
electrodes draws electrons toward a metal target (the anode). X-rays are
produced at the point of impact, and radiate in all directions.

xlix | P a g e
Dissolve 0.036 mol lead acetate, 0.142 mol
thiourea and 8.57 mmol CTAB into 40 mL, 20
mL and 20 mL deionized water, respectively.

Add thiourea and CTAB solutions


with lead acetate solution drop wise under
constant stirring condition.

Transfer the mixture to 100 mL Teflon lined


stainless steel auto clave.

Heat the auto clave to 180 °C for different


times (2 h, 4 h, 6 h and 12 h) and cool to
room temperature naturally.

Black color precipitate, centrifuged, washed


with distilled water and ethanol and dried.

Figure 2.1 Synthesis procedure for the fabrication of PbS crystals via
hydrothermal method.

l|Page
Dissolve 0.036 mol lead acetate, 0.142 mol
thiourea and 8.57 mmol CTAB into 40 mL, 20
mL and 20 mL deionized water, respectively.

Add thiourea and CTAB solutions with lead


acetate solution drop wise under constant
stirring condition.

Transfer the mixture to microwave vessel


and irradiated under microwave radiations
for 5 min.

Black color precipitate, centrifuged, washed


with distilled water and ethanol and dried.

Figure 2.2 Synthesis procedure for the fabrication of PbS crystals via
microwave method.

li | P a g e
If an incident X-ray beam encounters a crystal lattice, scattering occurs.
Although most scattering interferes with itself and is eliminated (destructive
interference), diffraction occurs when scattering in a certain direction is in
phase with scattered rays from other atomic planes. Under this condition the
reflections combine to form new enhanced wave fronts that mutually reinforce
each other (constructive interference). The relation by which diffraction occurs
is known as the Bragg law or equation:
2dsinθ = nλ (2.26)
here d is the spacing between diffracting planes, θ is the incident angle, n is any
integer, and λ is the wavelength of the beam. These specific directions appear
as spots on the diffraction pattern called reflections. Thus, X-ray diffraction
results from an electromagnetic wave (the X-ray) impinging on a regular array
of scatterers (the repeating arrangement of atoms within the crystal).

In Figure 2.3, the incoming beam causes each scatter to re-radiate a


small portion of its intensity as a spherical wave. If scatterers are arranged
symmetrically with a separation d, these spherical waves will be added
constructively only in the directions where their path difference 2dsinθ is equal
to an integral multiple of wavelength λ. In that case, part of the incoming beam
is deflected by an angle 2θ, producing a reflection spot in the diffraction
pattern.

The X-ray powder diffraction (XRD) pattern of the products were


recorded by employing a Bruker D8 advance X-Ray diffractometer with CuKα
radiation (λ =1.54 Ǻ). For recording the specra, powder samples were pressed
in a glass sample holder.

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Figure 2.3 A schematic representation of X-ray differaction from finite number
of planes.

liii | P a g e
When a material is irradiated with a parallel beam of X-rays, the atomic
lattice of the sample acts as a three dimensional diffraction grating causing the
X-ray beam to be diffracted to specific angles. The diffraction pattern, that
includes position and the intensities of the diffraction beam, provides lots of
information about the sample

Every crystalline material will give a characteristic diffraction pattern


which acts as a unique finger print of that material. The position (d) and
intensity (I) information are used to find the type of material by comparing
them with patterns for over 80,000 data entries in the International Powder
Diffraction File (PDF) database, complied by the Joint Committee for Powder
Diffraction Standards (JCPDS), By this method, identification of any
crystalline compounds can be made. Lattice parameter of sample can be
calculated as follow:

The inter planner spacing (d) of given sample can be calculated from
Bragg’s law

λ = 2 d sinθ (2.27)

where wavelength (λ) is known and theta (θ) is the half value of the peak
position, hence ‘d’ can be calculated.
The relationship between inter planner spacing (d) and lattice constant
for cubic crystal is given as:-

a
d (2.28)
h  l2  k2
2

where, h, k and l are the Miller indices of the peaks and ’a’ is lattice parameter
of sample.

The particle sizes (d) can be calculated using the Debye Scherrer
formula:
(2.29)
d = 0.9 λ/β cos θ

liv | P a g e
where, λ is the wavelength of the X-Ray, θ is the angle of reflection and β is the
full width of Bragg peak at half maximum.

Scanning Electron Microscopy (SEM)


A scanning electron microscope (SEM) is a direct and important tool for
imaging the nanoparticles. The high-resolution, three dimensional images can
be formed by SEM. They provide morphological, topographical and
compositional information for the science and industry applications. The SEM
is developed by Dr. Charles Oatlev with the assistance of graduate students in
1950s.
SEM is one of the electron microscopes which utilizes the same
principles as light microscopes. In optical microscopes, electromagnetic waves
of suitable wavelength scattered from the sample are detected using a system of
focusing lenses whereas in electron microscopes, electrons are used instead of
electromagnetic radiation and electrostatic or magnetic lenses are used rather
than glass lenses.
The concept of electron microscope was developed when de Broglie
proposed that particles can show wave characteristics. The wavelength
associated with electrons can be given by
h h
l  (2.30)
p mv
where, h is plank constant, p is momentum, m is mass of electron and v is the
velocity of electrons. With this prediction, an electron beam can be used in
electron microscopes in the same manner as the electromagnetic light is used in
optical microscopes. Advantages of using electrons are that their wavelength
can be tuned to a very small value, just by changing their energies and due to
very small wavelength (0.02- 0.05 nm), resolution is in the sub-nanometer
range.
When a fine focused beam of high energy electrons (20-30 KeV) strikes
the sample surface, a variety of emissions occur as shown in Figure 2.4.

lv | P a g e
Incident electron beam

X-rays Secondary electrons

Sample

Inelastically scattered electrons


Elastically scattered electrons
Transmitted electrons

Figure 2.4 Emission occurring from the sample after irradiation with electron
beam.

lvi | P a g e
The interaction between electrons and solids are quite complicated
because of charge on electrons and interaction with electrons and ions in solids.
Because of this interaction, high energy electrons are scattered in backward
direction, secondary electrons of low energy (< 50 eV) escape backwards and
X-rays are emitted. The result of this interaction depends upon the energy of
electrons, type of sample and thickness of sample. SEM uses backscattered
electrons from a sample for imaging.
A schematic diagram of SEM is shown in Figure 2.5. A focused beam of
electron is emitted from an electron gun and accelerated to high kinetic energy
using an anode at high positive potential. The electron beam travels through the
electrostatic and magnetic lenses which focus the electron beam to a very small
spot size ~ 0.01 µm. The highly focused electron beam strikes the sample
surface. The backscattered electrons leaving the sample are collected by
detectors and conveyed to amplifier. The output signals of this amplifier are fed
in to a cathode ray tube or a computer to form an image of sample surface.
SEM images have been recorded using a ZEISS, EVO 18 Scanning
electron microscope (SEM). Samples have been prepared by making films on
glass plates. In order to avoid the oxidation and contamination of filament in
addition to reduce the collisions between electrons and air molecules, filament
and sample have to be placed in vacuum chamber. Usually vacuum ~ 10 -5 torr
or more is necessary for a normal operation of SEM.
Most samples require some preparation before being placed in the
vacuum chamber. All water must be removed from the samples because the
water would vaporize in the vacuum. All metals are conductive and require no
preparation before being used. All non-metals are coated with a very thin metal
film like gold or platinum (< 10 nm) making them conducting without altering
any essential details of the sample.

lvii | P a g e
Figure 2.5 A schematic diagram of scanning electron microscope [13].

lviii | P a g e
UV-Vis Absorption Spectroscopy
The ultraviolet and visible spectrophotometry is one of the oldest and
still one of the more useful methods in most laboratories concerned with the
identification and measurement of organic and inorganic compounds in the
wide range of products and processes in food stuffs, pharmaceutical drugs,
fertilizers, mineral oils, nucleic acids and proteins. In every branch of
molecular biology and life sciences, the spectrophotometer is an essential aid to
both research and routine control.
The wavelength of light absorbed by a compound is characteristic of its
chemical structure. Specific regions of the electromagnetic spectrum are
absorbed due to excitation of specific type of atomic and molecular motion to
higher energy levels. The microwave radiation is generally absorbed due to
excitation of molecular rotation motion. Absorption of infrared radiation is
associated with vibrational motions of molecules. Absorption of visible and
ultraviolet (UV) radiation is associated with excitation of electrons to higher
energy levels, in both atoms and molecules. The visible spectrum is usually
considered to be 380-770 nm and the ultraviolet region is normally defined as
200-380 nm. The energies of visible and ultraviolet radiation are sufficient to
excite a molecular electron to a higher energy orbital. Consequently, absorption
spectroscopy carried out in this region is sometimes called “electronic
spectroscopy”.
Absorption spectra were recorded using Perkin Elmer Lambda 750 UV-
VIS-NIR spectrometer in the wavelength range of 200-800 nm at room
temperature. A working schematic of the UV-visible spectrophotometer is
shown in Figure 2.6.
In UV-vis spectrophotometer, the light source needs to cover the entire
visible and the near ultra-violet region (200-900 nm). Since it is not possible to
get this range of wavelengths from a single lamp, a combination of a deuterium
lamp for the UV region and tungsten or halogen lamp for the visible region is
used.

lix | P a g e
Figure 2.6 A schematic diagram of UV-Vis absorption spectrophotometer [14].

lx | P a g e
The beam of light coming from source is separated into its component
wavelength by diffraction grating. The function of slit is to send a
monochromatic beam into the next section of the spectrophotometer. Light
from the slit then falls onto a rotating disc.
Each disc consists of three different segments: an opaque black section,
a transparent section and a mirrored section. If the light hits the transparent
section, it will go straight through the sample cell, get reflected by a mirror, hits
the mirrored section of a second rotating disc, and then collected by the
detector. Else if the light hits the mirrored section, gets reflected by a mirror,
passes through the reference cell, hits the transparent section of a second
rotating disc and then collected by the detector. If the light hits the black
opaque section, it is blocked and no light passes through the instrument.
Finally, detector converts the light into a current signal that is read by
computer. Higher the current signal, greater is the intensity of light.
According to Beer-Lambert's Law, the absorption of light is directly
proportional to both the concentration of the absorbing medium and the
thickness of the medium in the light path.
Beer-Lambert's Law is expressed as
A= ε c b (2.31)
where A is absorbance, c is molar concentration, b is the thickness of the
medium (path length) and ε is molar absorptivity or molar absorption
coefficient. Thus absorption of photons after passing through a material can be
expressed as
A= log10(I\I0) = ε c b (2.32)
where, I is the intensity of the transmitted light and I o is the intensity of the
incident light.
The optical band gap of material can be determined by using Tauc plot.
According to Tauc’s law
( a hn )  k ( hn  Eg )
n
(2.33)
where, α is absorption coefficient, hν is the incident photon energy, k is
constant and n = 1/2 for direct band gap materials and n=2 for indirect band

lxi | P a g e
gap materials. The energy intercept of a plot of (αhν)2 versus hν, yields Eg for a
direct allowed transition.
Raman spectroscopy
Raman spectroscopy is frequently used tool for determining the compositions
of solids, liquids and gases by studying low frequency modes of atomic and
molecular systems of sample. Such low frequencies fall generally in the range
associated with the rotational, vibrational and electronic level transitions
involved in these systems. Raman scattering (or the Raman effect) was
discovered by Sir Chandrasekhra Venkata Raman in 1928 who won the Nobel
prize for his work. According to Raman, if any substance (gaseous, liquid or
solid) is exposed to radiation of definite frequency, then the light scattered at
right angles contains frequency different from that of incident radiation, and is
the characteristic of the substance under examination. Thus the phenomenon
due to which the scattering light has a slight different frequency from that of
incident radiation and there is a change in the atomic oscillations within the
molecules is called Raman effect. Raman also observed that difference Δν
between the incident and any given scattered line was constant and
characteristic of the substance irradiated, and doesn’t dependent on the
frequency of incident radiation.
There are two types of Raman scattering, namely Stokes scattering and
anti-Stokes scattering. When the energy of the incident photon is not enough to
excite the molecule from the ground state to the lowest electronic state, the
molecule will be excited to a virtual state lying between ground and lowest
electronic state. The electron in the excited molecule cannot stay long in the
virtual state and will then immediately go back to the ground state. If the
electron comes back to its original state, then the frequency of the emitted
photon is same as that of the incident photon. Such a scattering phenomenon is
known as Rayleigh scattering. On the other hand, there is one more possibility
for the electron to go to a virtual state that is different from where it is excited
which gives an energy difference between the emitted photon and the incident
photon, then the frequency of emitted photon is different from that of incident

lxii | P a g e
photon. This kind of scattering is known as Raman scattering. If the emitted
photon has energy smaller than that of the incident photon, scattering process is
known as Stokes scattering and if the energy of incident photon is higher than
that of emitted photon, it is known as anti-Stokes scattering. Figure 2.7
illustrates the differences between Rayleigh scattering, Stokes scattering and
anti-Stokes scattering in the quantum mechanical point of view.
The Raman spectrum is basically a recording of the frequency and
intensity of the inelastically scattered photons. Since every atom and molecule
possess its own Raman spectrum, which can be used to figure out its atomic
and molecular structure and identify elements that are present in the sample
being to be study. In the present work, Raman spectra were recorded with
Deltanu advance Raman spectrometer using a 532 nm laser beam.
A simple classical electromagnetic field theory can be used to explain
many of the important features of Raman band intensities. The incident light
wave represented by an electric field E induces a dipole moment in the
molecules. The induced dipole moment P is given by
P = αE (2.34)
where, α is the polarizability of the molecule, and the theory of Raman effect of
scattering highly depends upon this factor. The polarizability measures the ease
with which the electron cloud around a molecule can be distorted. If the
variations in distances between atoms in the scattered molecules are negligible,
then the frequency of incident and scattered radiations will be same and the
scattering will be Rayleigh’s scattering. But if the interatomic distances in the
scattered molecules are appreciable, a condition of anisotropy or polarizability
takes place and the consequent vibrational frequencies of the scattered
molecules (called Raman frequencies) are superimposed on the fundamental
frequency of the incident radiation.

lxiii | P a g e
Figure 2.7 A schematic representation of Rayleigh scattering, Stokes scattering
and anti-Stokes scattering.

lxiv | P a g e
Thus, the change is described by the polarizability derivative; dα/dQ, the
Raman scattering occurs because a molecular vibration can change the
polarizability. The selection rule for a Raman-active vibration is
(2.35)
≠0

i.e. there should be a change in polarizability during the vibration. If the


symmetry of molecule is such that this condition is fulfilled, then the transition
is said to be allowed or Raman active; if it is not fulfilled, then it is said to be
forbidden or Raman inactive.
Fourier Transform Infrared Spectroscopy (FTIR)
Fourier transform infrared spectrometer (FTIR) is very important for
finding presence of chemical bonds in the sample. It detects the vibration
characteristics of chemical functional groups in the sample. This technique is
used for those molecules that have permanent dipole moment in them.
Homonuclear molecules like H2, N2, O2 etc. have zero dipole moment and do
not interact with infrared radiation, whereas hetronuclear molecules such as
HCl interact with infrared radiation.
All spectroscopy methods are based on the interplay of electromagnetic
radiation with a medium or the measurement of radiation emitted from the
medium. Electromagnetic radiation can be characterized by its energy,
wavelength, frequency or wavenumber.
Infrared radiation is electromagnetic radiation which has range of
wavenumbers from 13300 cm-1 to 3.3 cm-1. Usually the infrared region is
divided into three regions: near-infrared (13300-4000 cm -1), middle-infrared
(4000-200 cm-1) and far-infrared (200-3.3cm-1) regions. Organic compounds
have fundamental vibration bands in the mid infrared region, that’s why this
region is commonly used in infrared spectroscopy. Each substance has its
unique infrared spectrum; hence this spectrum can be used as an unbiased
characteristic to identify the sample.

lxv | P a g e
When infrared light strikes the sample, interaction between radiation and
matter takes place and because of this interaction, the chemical bonds of matter
undergo changes in stretching, bending, rotation, twisting or rocking vibration
modes. Consequently chemical functional groups tend to exhibit changes in the
specific wavenumber range.
The infrared spectrometers can be classified into two groups: Dispersive
infrared spectrometer (IR) and Fourier transform infrared spectrometer (FTIR).
The main advantage of FTIR over the conventional IR spectrometer is its
speed. In dispersive IR spectrometer, either grating or prism is used as a
monochromator to disperse the radiation of polychromatic source into different
spectral elements, which are sequentially measured by detector, one element at
each time. Only one element of radiation is measured at each time hence
sampling is slow in dispersive IR spectrometer. FTIR spectrometer does not
have any monochromator to select wavelengths while it has an interferometer
to generate an interferogram. In FTIR spectrometer, all wavelengths are
measured simultaneously which results in faster sampling.
In the present work, FTIR spectra were recorded using Agilent Carry
600 FTIR spectrometer. The potassium bromide is well salt for the
measurement of mid infrared because it does not have any absorption in this
region. Therefore the sample tablets were prepared in KBr. The tablets were
prepared by using 100 mg of pure dry KBr powder and 1 mg of sample.
A schematic diagram of FTIR spectrometer is shown in Figure 2.8.
FTIR spectrometer makes use of the Michelson interferometer for recording
the spectra. FTIR spectrometer has a source which is a filament maintained at
red or white heat by passing electric current. Usually glober filament (rod of
corborundum i.e. SiC) or Nernst filament (spindle of rare earth oxide) are
used. When radiation from source strikes the beamsplitter, incoming beam is
splitted into two optical beams which travel to two mirrors (one fixed and
other movable). These two beams are reflected back from both the mirrors
along the same path and recombine again at the beam splitter.

lxvi | P a g e
Figure 2.8 A schematic diagram of FTIR spectrometer [15].

lxvii | P a g e
These two beams interfere constructively or destructively at the beam
splitter, it depends on the path lengths of the rays. This combined beam falls
on the sample. The beam after interaction with sample arrives at the detector
and this detected interferogram is applied to a mathematical operation known
as Fourier Transformation. This transformation converts time domain signals
into a frequency domain spectrum. Thus an FTIR spectrum obtained is a plot
of absorbance (or transmittance) versus wavenumber.
Fluorescence Spectroscopy
Fluorescence spectroscopy is that characterization technique which
measures emission of radiation by a material. It records the intensity of light
radiated from material as a function of wavelength. It is mainly concerned with
electronic and vibrational states.
In fluorescence spectroscopy, sample gets excited from ground
electronic state to one of the different vibrational states in the excited state by
absorbing photon of appropriate wavelength. Once the molecule is in excited
state, relaxation occur due to collisions with other molecules, hence excited
molecule reaches the lowest vibrational state of the excited electronic state by
losing vibration energy. Further the molecule emits photon and drops down to
one of the various vibrational levels of the ground electronic state.
Since molecules may drop down into anyone of various vibrational
levels of ground state, hence emitted photon may have different energies and
thus different frequencies. Therefore, the structure of the different vibrational
levels can be determined by analyzing the different frequencies of light emitted
in fluorescence spectroscopy, along with their relative intensities.
A Schematic diagram of fluorescence spectrophotometer is shown in
Figure 2.9. A source of light which can produce radiation ranging from
UV(~200 nm) to IR (~800 nm). A filter to throw away large band of
wavelengths, monochromators or wavelength selectors, sample holder, a
detector and a recording system have to be in fluorometer.

lxviii | P a g e
Figure 2.9 A schematic diagram of Flurospectrometer [16].

lxix | P a g e
In the present work, Photoluminescence (PL) measurements were
carried out on a Perkin Elmer LS45 fluorescence spectrophotometer using
335.2 nm excitation wavelengths.
2.3 Conclusion
The conclusions of this chapter are as follows:
(i) Theoretical details of CRYSTAL06 code used to calculate the structural,
optical and electronic properties of lead-chalcogenides are discussed.
(ii) Synthesis methods (hydrothermal and microwave routes) of PbS crystals
are explained.
(iii) Various spectroscopic, microscopic and diffraction techniques used for
characterization of samples are briefly discussed.

lxx | P a g e
References

[1] V.R. Saunders, R. Dovesi, C. Roetti, M. Causµa, N.M. Harrison, R. Orlando and
C.M. Zicovich-Wilson, CRYSTAL06 User's manual (University of Torino, 2006).

[2] P. Hohenberg and W. Kohn, Inhomogeneous Electron Gas, Phys. Rev. 136 (1964)
B864.

[3] W. Kohn and L. Sham, Self-Consistent Equations Including Exchange and


Correlation Effects, Phys. Rev. 140 (1965) A1133.

[4] P.A.M. Dirac, Quantum Mechanics of Many-Electron Systems, Proc. R. Soc. A 123
(1929) 792.

[5] D.M. Ceperley and B.J. Alder, Ground State of the Electron Gas by a Stochastic
Method, Phys. Rev. Lett. 45 (1980) 566.

[6] S.H. Vosko, L. Wilk and M. Nusair, Accurate spin-dependent electron liquid
correlation energies for local spin density calculations: a critical analysis, Can. J.
Phys. 58 (1980) 1200.

[7] J.P. Perdew and Y. Wang, Accurate and simple density functional for the electronic
exchange energy: Generalized gradient approximation, Phys. Rev. B 33 (1986) 8800.

[8] A.D. Becke, Density‐functional thermochemistry. III. The role of exact exchange,
J. Chem. Phys. 98 (1993) 5648

[9] F. Brich, Finite elastic strain of cubic crystals, J. Geophys. Res. 83 (1978) 1257.

[10] J.P. Poirer, Introduction to the Physics of Earth’s Interior, Cambridge University
Press, Cambridge, 27 (1992) 193.

[11] M.J. Cooper, Compton scattering and electron momentum determination, Rep.
Prog. Phys. 48 (1985) 415.

[12] M.J. Cooper, P.E. Mijnarends, N. Shiotani, N. Sakai and A. Bansil, X-Ray
Compton Scattering (Oxford: Oxford Publishing Press), (2004).

[13] www. Innerfidelity.com.

[14] www. Chemguide.co.uk.

[15] en.wikipedia.org.

[16] cnx.org

lxxi | P a g e
Chapter 3

Structural properties of PbX (X=S,


Se, and Te)

lxxii | P a g e
3.1 Introduction
The study of lead chalcogenides (PbS, PbSe and PbTe) is the subject of
extensive research due to their interesting and remarkable structural properties.
The PbX (X=S, Se and Te) compounds and their alloys have been shown to be
the most efficient thermoelectric materials for power generation in the wide
temperature range [1-2].
The PbX compounds crystallize in the rocksalt structure at normal
temperature and pressure. Knowledge of the structural properties of PbX under
pressure is important in the semiconductor device industry. Since last few
decades, structural phase transition in PbX under high pressure have been
getting a great attention due to its unknown intermediate phase.
There are considerable experimental and theoretical studies on the high
pressure phase transition of PbX. The structural phase transformations in PbX
compounds first reported by Bridgman [3]. Chattopadhyay et al [4] studied the
high pressure phase transition in PbX experimentally. They performed high
pressure X-ray diffraction experiments on PbX upto 300 Kbar with synchrotron
radiation. They found that the PbS, PbSe and PbTe undergo pressure induced

first-order structural phase transition from NaCl-type (B1, Fm m) phase to an


intermediate phase at about 22, 45 and 60 Kbar respectively. Further, structural
phase transition for PbS, PbSe and PbTe from intermediate phase to CsCl-type

(B2, Pm m) phase occur at about 215, 160 and 130 Kbar respectively. They
reported the intermediate phase of PbX is TlI-type (B33, Cmcm) phase. Knorr
et al [5] investigated the high pressure behavior of PbS by angular dispersive
X-ray powder diffraction upto pressure 6.8 GPa. They concluded that the PbS
crystallizes in NaCl-type (B1) phase at ambient conditions and undergoes
structural phase transition from NaCl-type (B1) phase to CrB-type (B33,
Cmcm) phase. Steltov et al [6] performed a synchrotron study of the
intermediate phase of PbSe and found FeB-type (Pnma, B27) phase as a
intermediate phase of PbSe. Rousse et al [7] evaluated the structure of the
intermediate phase of high pressure and reported PbTe has an orthorhombic

lxxiii | P a g e
Pnma structure between 6 and 16 GPa, which is a modulated deformation of
the low-pressure NaCl structure.
Tolendano et al [8] have presented a phenomenological model,
consisting of two consecutive displacive mechanisms, coupled to tensile and
shear strain, for the transformation between the B1 and B2 type phases. These
mechanisms lead to intermediate structures of the TlI (Cmcm, B33) or GeS-
type (Pbnm, B16) phase. Shchennikov et al [9] analyzed the structure of
intermediate phase of PbTe by the synchrotron radiation diffraction method and
determined the orthorhombic structure (Pnma) as the intermediate phase of
PbTe. Maclean et al [10] carried out the high pressure angle dispersive X-ray
powder diffraction studies on the PbX semiconductors using image plate
detection and suggested that the intermediate structure is monoclinic for all
PbX, which opposes to the previously accepted orthorhombic structure for
PbX.
Mariano and chopra [11] investigated the Pnma orthorhombic structure
as the intermediate phase of PbX. Wei et al [12] obtained the phase relations
and pressure volume dependences using the exterior heating diamond anvil cell
(DAC) technique at pressure up to 19.0 GPa and in the temperature range 300-
653 K. They concluded that the phase transition for PbX takes place at 2.4 GPa
approximately. Ovsyannikov et al [13] studied the phase transitions in PbSe
under the actions of fast neutron bombardment and pressure and observed the
phase transition from NaCl to GeS phase under pressure.
Ponosov et al [14] investigated pressure-induced structural phase
transition in PbX compounds by Raman scattering. They observed number of
Raman modes for the intermediate phase of PbX. These modes were found
significantly smaller than expected from selection rules for the GeS type but
seem to be consistent with the TlI type. Grzechnik and Friese [15] studied the
pressure-induced crystal structure of PbS above 2.2 GPa with single crystal X-
ray diffraction in a diamond anvil cell at room temperature. They reported that
PbS undergoes a phase transition from NaCl type to TlI above 2.2 GPa, in
which the Pb atoms are surrounded by seven S atoms in a capped trigonal

lxxiv | P a g e
prism coordination. Fujii et al [16] examined the high pressure phase transition
of PbTe. They reported that PbTe undergoes transition from NaCl-type to GeS-
type structure at 4.5 GPa then, from GeS-type to CsCl-type structure at 16±
1GPa. Ves et al [17] also investigated GeS structure as intermediate phase of
PbTe. The effect of grain size on the pressure induced phase transitions in PbS
investigated by Qadri et al [18] and Jiang et al [19].They reported the onset of
transition pressure increases with decreasing particle size.
To know the actual intermediate phase of PbX, several first-principles
calculations were also made by variety of methods. Wei and Zunger [20]
calculated equilibrium lattice constants, bulk modulus and first order pressure
derivatives of the bulk modulus using the LDA as implemented by the general
potential linearized augmented plane-wave (LAPW). Hummer et al [21]
presented ab-initio calculations on the structural properties of PbX using
different basis sets like FP-APW+lo and PAW and different exchange
functional like PBE-GGA and the hybrid HSE03.They compared their results
with experiment and found that the computed structural parameters using the
hybrid functional HSE03 are in better agreement with available experimental
results. Ahuja [22] studied the high pressure structural phase transitions in PbX
by means of first-principles total energy calculations within the GGA
approximation using the full potential linear-muffin-tin-orbital (FP-LMTO)
method. He reported that the PbX are stable in NaCl-type structure at ambient
conditions and transform to CsCl-type structure at high pressure through an
intermediate (TlI-type) phase and explored the structural parameters of PbX in
NaCl-type, TlI-type and CsCl-type phases. He found that the calculated
transition pressure, equilibrium volumes and bulk moduli were in good
agreement with previously reported results. Zagorac et al [23] performed a
structure prediction study for PbS at different pressures using LCAO method
under different approximations like HF, DFT-B3LYP and DFT-LDA. They
found transitions from NaCl-type to the TlI-type phase at 4.5 GPa and from
TlI-type phase to CsCl-type at 25 GPa.

lxxv | P a g e
P. Bhardwaj [24] have investigated the structural and mechanical
properties of PbS by applying three body potential (TBP) model. Using the FP-
LMTO method based on DFT within GGA, high pressure phase transition of
PbS has been investigated by Bencherif et al [25]. They have suggested that
PbS undergoes a structural phase transition from NaCl-type to Pnma-type
phase at 8.13 GPa; further structural phase transition from this intermediate
phase to CsCl phase at 18.76 GPa has been investigated. They have calculated
structural parameters like equilibrium lattice constants, bulk modulus and first
order pressure derivatives of the bulk modulus for PbX , which are in good
agreement with experiment.
From the above reviews, it is clear that the intermediate phases of PbX
between NaCl-type and CsCl-type phases are not certain. Considering all the
controversies related to the pressure-induced intermediate phase of PbX, the
study of the high pressure phase transition of PbX is considered.
The organization of this chapter is as follows: In section 3.2 the
computational approach is described. The structural data are presented in
section 3.3. A conclusion of work is given in section 3.4.
3.2 Computational details

The ab-initio periodic LCAO calculations have been performed using


quantum mechanical CRYSTAL06 [26] code. The LCAO calculations have
been performed wherein one solves the Kohn-Sham equations self-consistently
under the DFT [27]. This code includes various schemes for constructing the
Hamiltonian for the periodic solids. The HF approximation [28] and the DFT
[27] are the well-known approaches among these schemes. The all electron
basis set for Pb, S, Se and Te have been taken from http://www.crystal.unito.it
and http://www.tcm.phy.cam.ac.uk/. The present calculations have been
performed in the frame work of DFT. For the first-principles total energy
calculations, the LCAO method within both LDA and GGA schemes have been
employed.

lxxvi | P a g e
Within LDA, the exchange scheme of Becke [29] and correlation
functional of von Barth- Hedin (VBH) [30] have been considered in the
computation. Within GGA, the exchange scheme of Becke [29] and correlation
functional of Perdew-Burke-Ernzerhof (PBE) [31] have been considered.
The self –consistent calculations have been performed considering 29 k
points in the irreducible Brillouin zone with sufficient tolerances. To achieve
self-consistency, 70% mixing of successive cycles is considered and self
consistency is achieved within 10 cycles.
The cohesive energy from the Compton profile data can be derived as
follows [32]

Ecoh  � J (
p �

2
z s pz )  J fa ( pz ) �
�dpz (3.1)
0

where Js and Jfa represent Compton profiles of solid and free atoms,
respectively. The solid Compton profile (Js) values are calculated from DFT-
LCAO method and the free-atom Compton profile (Jfa) values are taken from
Biggs et al [33].
3.3 Results and Discussion
3.3.1 Structural properties
The structural parameters like lattice parameter (a), bulk modulus (B 0),
and its pressure derivatives (B0') for PbX compounds in B1, B27 and B2 phases
were computed using GGA and LDA schemes, then results obtained by both
the approximations are compared mutually and with previously reported
theoretical and experimental results. In order to calculate, the ground state
properties, the total energies for PbX compounds computed over a set of
different volumes around the equilibrium value and then fitted to the third order
Birch-Murnaghan [34, 35] equation of state (EOS).
The variations of the total energy versus volume for these compounds
are presented in Figures 3.1-3.3 (3.4-3.6) with GGA (LDA). At equilibrium
volume, the total energy per formula unit of B1 phase is lower than the other

lxxvii | P a g e
phases for all PbX compounds, indicating that B1 phase is stable phase for PbX
compounds.
The calculated values of lattice constant for PbS, PbSe and PbTe in B1 phase
with GGA (LDA) are 5.89, 6.08 and 6.462 Å (5.99, 6.17 and 6.512 Å). The
LDA gives the higher value of equilibrium lattice constant for PbX compounds
as compared with the GGA approximation. For PbS and PbSe, the calculated
lattice constant with GGA (LDA) approximation are slightly overestimated
(underestimated) to the experimental result of Chattapadhyay et al [4],
Modelung et al [37] and Dornhaus et al [38]. Lattice constant for PbTe,
calculated with GGA is exactly same as experimental result of Modulung et al
[38] and calculated with LDA is slightly overestimated to the experimental
values of [4] and [7]. The calculated bulk modulus for PbX compounds with
both approximations are slightly overestimated as compared to the
experimental results.
The calculated values of lattice constant for PbS, PbSe and PbTe in B2
phase with GGA (LDA) are 3.559, 3.709 and 3.90 Å (3.64, 3.74 and 3.90 Å).
While calculating lattice parameters for PbX compounds in B2 phase, GGA
gives lower values than LDA. For all PbX compounds, the calculated lattice
constants with both approximations are slightly overestimated to the
experimental result of Chattapadhyay et al [4].
The calculated structural parameters for PbS, PbSe and PbTe are
reported in Tables 3.1-3.3, respectively and compared with previous
experiments and other computed results. From Tables 3.1-3.3, it is clearly
visible that bulk modulus of PbX compounds in stable phase decreases from
PbS to PbTe. Thus PbTe is more compressible as compared to the other two
compounds because it has smallest bulk modulus.

lxxviii | P a g e
-0.5

-1.0

-1.5

-2.0

-2.5
B2
Energy (eV)

-3.0

-3.5

-4.0
B1
B27
-4.5

-5.0
30 35 40 45 50 55 60 65 70 75 80
3
Volume (Å )

Figure 3.1 First-principles energy volume curves for B1, B27 and B2 phases of
PbS using the PBE correlation functional. The scattered points show calculated
energies and the solid lines show the fitted E(V) curves according to Birch-
Murnaghan equation of state (EOS).

lxxix | P a g e
0

-1
Energy (eV)

-2

-3 B27
B2
B1

-4

40 50 60 70 80
3
Volume (Å )

Figure 3.2 First-principles energy volume curves for B1, B27 and B2 phases of
PbSe using the PBE correlation functional. The scattered points show
calculated energies and the solid lines show the fitted E(V) curves according to
Birch-Murnaghan equation of state (EOS).

lxxx | P a g e
2
Energy (eV)

B2

B27

B1
-2
40 45 50 55 60 65 70 75 80 85 90
3
Volume (Å )

Figure 3.3. First-principles energy volume curves for B1, B27 and B2 phases
of PbTe using the PBE correlation functional. The scattered points show
calculated energies and the solid lines show the fitted E(V) curves according to
Birch-Murnaghan equation of state (EOS).

lxxxi | P a g e
-2.0
-2.2
-2.4
-2.6
-2.8
-3.0
-3.2
Energy (eV)

-3.4
-3.6
-3.8
B2
-4.0
-4.2
-4.4
B27
-4.6 B1
35 40 45 50 55 60 65
3
Volume (Å )

Figure 3.4 First-principles energy volume curves for B1, B27 and B2 phases of
PbS using the VBH correlation functional. The scattered points show calculated
energies and the solid lines show the fitted E(V) curves according to Birch-
Murnaghan equation of state (EOS).

lxxxii | P a g e
-1.0

-1.5

-2.0

-2.5
Energy (eV)

B2
-3.0

-3.5 B27

-4.0
B1

-4.5
35 40 45 50 55 60 65 70 75 80 85
3
Volume (Å )

Figure 3.5 First-principles energy volume curves for B1, B27 and B2 phases of
PbSe using the VBH correlation functional. The scattered points show
calculated energies and the solid lines show the fitted E(V) curves according to
Birch-Murnaghan equation of state (EOS).

lxxxiii | P a g e
2

0
Energy (eV)

-1

-2 B2

B27
-3
B1

40 50 60 70 80

3
Volume (Å )

Figure 3.6 First-principles energy volume curves for B1, B27 and B2 phases of
PbTe using the VBH correlation functional. The scattered points show
calculated energies and the solid lines show the fitted E(V) curves according to
Birch-Murnaghan equation of state (EOS).

lxxxiv | P a g e
Table 3.1
Calculated and experimental lattice parameter (a), bulk modulus
(B0), its pressure derivatives (B0') and cohesive energy (Ecoh) for PbS.
Present Experimental Other calculations
B1 GGA LDA
a (Å) 5.89 5.99 5.940[4], 5.906[20], 6.012[21],
5.936[37],
6.006[22], 5.86[23],
5.929[38,41]
6.0[25]
Bo 67.9 64.06 62.8[37], 66.3[20], 52[21],
(GPa) 62.2[38] 56.0[22], 54.63[25]
Bo’ 3.9 4.1 - 4.38[20], 3.6[22],
4.10[25],
Ecoh 7.52 - 7.6[39],7.47[40]
(eV)
B2
a (Å) 3.559 3.64 3.379[4] 3.54[23]
B0 78 70.71 - 59.0[22]
(GPa)
B0' 4.3 3.8 - 3.6[22]
B27
a (Å) a=7.97 a=8.07 - a=7.75,b=4.35,c=6.04[25],
b=4.19 b=4.29 a=7.92,b=4.14,c=5.93[23],
c=5.98 c=6.08
B0 70.02 63.93 - -
(GPa)
B0' 3.9 3.8 - -
B33
a (Å) a=4.05 a=4.35 a=3.83 a=4.06, b=11.33, c=4.18
b=11.35 b=11.2 b=10.39 [23]
c=4.2 c=4.05 c=4.01[4]
B0 83.96 57.5 - -
(GPa)
B0' 4.9 3.8 - -

lxxxv | P a g e
Table 3.2
Calculated and experimental lattice parameter (a), bulk modulus (B 0), its
pressure derivatives (B0') and cohesive energy (Ecoh) for PbSe.

Present Experimental Other calculations

B1 GGA LDA
a (Å) 6.08 6.17 6.133[4], 6.098[20], 6.226[21],
6.117[11], 6.214[22], 6.211[25]
6.124[37],
6.117[38,41]

Bo 66.96 64.72 28.8[36], 60.8[20], 44.5[21],


(GPa) 54.1[37], 49.5[22], 48.27[25]
54.1[38],

Bo’ 4 3.7 4.1[36] 4.56[20], 3.64[21],


3.8[22], 4.35[25],

Ecoh 6.95 - - 7.22[39], 7.25[40]


(eV)
B2
a (Å) 3.709 3.74 3.379[4] -
B0 70 64.72 - 62.0[22]
(GPa)
B0' 3.9 3.7 - 2.4[22]
B27
a (Å) a=11.38, a=11.48, a=11.61, b=4.00, a=8.07, b=4.49,
b=4.374, b=4.474, c=4.39[11] c=6.29[25]
c=4.259 c=4.359
B0 68.94 65.5 - -
(GPa)

lxxxvi | P a g e
B0' 4.9 4.9 - -

Table 3.3
Calculated and experimental lattice parameter (a), bulk modulus (B 0), its
pressure derivatives (B0') and cohesive energy (Ecoh) for PbTe.

Present Experimental Other calculations

B1 GGA LDA
a (Å) 6.462 6.512 6.458[4], 6.582[20], 6.439[21],
6.34[7], 6.566[22], 6.554[25]
6.462[37,41],
6.443[38]
Bo 49 49.97 48.5[7], 37.5[20], 51.7[21], 41.0[22],
(GPa) 38.9[36], 39.95[25]
39.8[37],
41.1[38]
Bo’ 4.1 4.1 - 4.27[20], 4.52[21], 4.0[22],
4.32[25]

Ecoh 7.41 - - 6.86[39], 6.88[40], 7.5[42],


(eV)
B2
a (Å) 3.90 3.95 3.570[4] -
B0 56.35 56.21 38.1[36] 41.0[22]
(GPa)
B0' 4.3 4.3 - 4.6[22]
B27
a (Å) a=8.4 a=8.52 a=8.177, a=8.53, b=4.70, c=6.72[25]
27, , b=4.495,
b=4.7 b=4.84 c=6.230[7]
45, ,

lxxxvii | P a g e
c=6.4 c=6.58
80 0

B0 54.64 48.83 - -
(GPa)
B0' 4.25 4.2 - -

The pressure and normalized volume curves for PbX compounds are
also plotted in Figures 3.7-3.9 (in Figures 3.10-3.12) with GGA (LDA). These
indicate that volume decreases smoothly with increasing pressure. In general,
the calculated structural results are in good agreement with previously reported
experimental and theoretical data.
To find the effect of pressure on bonding strength of lead chalcogenides,
the cohesive energy of PbS (in B1phase) has been computed at different
pressures and presented in Table 3.4. The variation in cohesive energy of PbS
under pressure is shown in Figure 3.13 which shows that the cohesive energy
of PbS decreases with increasing pressure. Since the cohesive energy is the
measure of bonding strength, hence it is clear that with increasing pressure,
bonding strength of PbS decreases.

3.3.2 Phase transition


In order to determine the transition pressure, the Gibbs free energy (G =
Eo + PV - TS) is used. Figures 3.14-3.16 and 3.17-3.19 present the variation in
the difference between enthalpy of PbX in (B2 and B27) and stable (B1) phases
as a function of pressure, within GGA and LDA, respectively. In this work,
zero temperature is considered. At this temperature the thermodynamically
stable phase is that one which has lowest enthalpy, H = E + PV at a given
pressure. When the enthalpy of the lower pressure phase coincides with that of
other phase, the transition from one phase to another phase occurs.
From Figures 3.14-3.16 (GGA approach), it is shown that PbS, PbSe
and PbTe exhibit a transition from NaCl phase to an orthorhombic Pnma (B27,
FeB type) phase at 2.56, 6.24 and 6.77 GPa, respectively, and further transition

lxxxviii | P a g e
from Pnma phase to the CsCl type (B2) phase is observed at 27.04, 16.39 and
13.04 GPa, respectively. Figures 3.17-3.19 (LDA approach) illustrated
transitions of PbS, PbSe and PbTe from NaCl phase to an orthorhombic Pnma
(B27, FeB type) phase at 4.7, 7.97 and 8.78 GPa, respectively, and from Pnma
phase to the CsCl type (B2) phase at 22.3, 18.25 and 15.19 GPa, respectively.

52

50 B1

48

46

44

42 B27
V (Å 3 )

40

38

36
B2
34

32
0 5 10 15 20 25 30 35 40 45 50

P (GPa)

Figure 3.7 The pressure-volume dependency for PbS using the PBE correlation
functional.

lxxxix | P a g e
55
B1

50

B27
V (Å 3)

45

40
B2

35
0 10 20 30 40 50

P (GPa)

Figure 3.8 The pressure-volume dependency for PbSe using the PBE
correlation functional.

xc | P a g e
65
B1

60

B27
55
V (Å 3 )

50

45 B2

40
0 10 20 30 40 50

P (GPa)

Figure 3.9 The pressure-volume dependency for PbTe using the PBE
correlation functional.

xci | P a g e
54

52

50 B1
48

46
B27
V (Å )

44
3

42

40

38
B2
36

34

0 10 20 30 40 50
P (GPa)

Figure 3.10 The pressure-volume dependency for PbS using the VBH
correlation functional.

xcii | P a g e
55
B1

50

B27
V (Å 3 )

45

40
B2

35
0 10 20 30 40 50

P (GPa)

Figure 3.11 The pressure-volume dependency for PbSe using the VBH
correlation functional.

xciii | P a g e
70
68
66
64 B1
62
60
58
56
V (Å 3)

B27
54
52
50
48
46
B2
44
42
0 10 20 30 40 50

P (GPa)

Figure 3.12 The pressure-volume dependency for PbTe using the VBH
correlation functional.

xciv | P a g e
Pressure E coh(eV)
(GPa)
Our Calculation Other calculations
0 7.52058 7.6 [39], 7.47 [40]
5 6.88083
10 6.46231
Table 15 5.99154 3.3
20 5.54336

Cohesive energy of PbS (B1 phase) at different pressures.

xcv | P a g e
7.5

7.0
E coh (eV)

6.5

6.0

5.5

0 5 10 15 20
Pressure (GPa)

Figure 3.13 The variation of cohesive energy of PbS (B1 phase) under
pressure. The solid line shows the linear fit and the dotted line shows the
calculated values.

xcvi | P a g e
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
B1
0.0
 H (eV)

-0.2 B27
-0.4
-0.6
-0.8
-1.0
-1.2 B2
-1.4
-1.6

0 10 20 30 40 50

P (GPa)

Figure 3.14 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbS using the PBE correlation functional.

xcvii | P a g e
0.8

0.6

0.4

0.2

B1
 H(eV)

0.0

-0.2

-0.4

-0.6 B27
B2
-0.8
0 10 20 30 40 50
P (GPa)

Figure 3.15 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbSe using the PBE correlation functional.

xcviii | P a g e
0.8

0.6

0.4

0.2
B1
0.0
 H(eV)

-0.2

-0.4

-0.6
B27

-0.8

-1.0
B2

0 10 20 30 40 50

P (GPa)

Figure 3.16 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbTe using the PBE correlation functional.

xcix | P a g e
0.8

0.6

0.4

0.2

0.0 B1
 H (eV)

-0.2
B27
-0.4

-0.6

-0.8
B2
-1.0
0 10 20 30 40 50

P (GPa)

Figure 3.17 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbS using the VBH correlation functional.

c|Page
1.2

1.0

0.8

0.6

0.4

0.2
B1
0.0
 H(eV)

-0.2

-0.4

-0.6 B27

-0.8

-1.0

-1.2 B2
-1.4
0 10 20 30 40 50
P (GPa)

Figure 3.18 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbSe using the VBH correlation functional.

ci | P a g e
1.0
0.8
0.6
0.4
0.2
B1
0.0
-0.2
-0.4 B27
 H (eV)

-0.6
-0.8
-1.0
-1.2
-1.4 B2
-1.6
-1.8

0 10 20 30 40 50

P (GPa)

Figure 3.19 Enthalpy calculated from first-principles total energy for the B1,
B27 and B2 structures of PbTe using the VBH correlation functional.

cii | P a g e
Table 3.5
Transition pressure (in GPa) for PbS, PbSe and PbTe.

Transition Present Experimental Other


calculations
GGA LDA
PbS B1 B27 2.56 4.7 2.2[4], 9.5[22],
2.2[36] 4.5[23], 8.13[25]
B27 B2 27.04 22.3 21.5[4], 25.0[22],
21.5[36] 25.0[23],
25.30[25],
PbSe B1 B27 6.24 7.97 4.5[4], 10.0[22],
4.5[36] 7.45[25]
B27 B2 16.39 18.25 16.0[4], 20.0[22],
16.0[36] 18.76[25]
PbTe B1 B27 6.77 8.78 6.0[4], 5.40[10], 9.0[22]
6.9[7],
4.5[16],
6.0[36]

B27 B2 13.04 15.19 13.0[4], 15.43[10],


17.3[7], 14.0[22]
16±1[16],
13.0[36]

ciii | P a g e
The present transition pressures for PbX compounds are given along with
previous results in Table 3.5. The transition pressures derived from GGA are
closer to experimental results as compared with LDA.
3.4. Conclusions
The ab-initio study of structural properties of PbS, PbSe and PbTe are
reported in this chapter. The results can be summarized as follows:
(i) The variations of the total energy versus volume for PbX compounds show
that B1 phase is the most stable phase for these compounds.
(ii) The intermediate phase of PbX between B1 and B2 phases is found to be
FeB type (B27, Pnma) phase.
(iii) The calculated structural parameters and transition pressures of PbX
compounds are in good agreement with previously reported experimental and
theoretical results.
(iv)The compressibility of PbTe is higher than that of other two compounds.
(v) Bonding strength of PbX decreases under pressure.

civ | P a g e
References

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cviii | P a g e
Chapter 4

Chapter 4

Pressure dependent electronic and optical


properties of lead chalcogenides
Chapter 4

4.1 Introduction
The study of electronic and optical properties of lead chalcogenides PbX
(X= S, Se, Te) have been subject of great interest for a long time on account of
a number of fascinating properties like high carrier mobility, high dielectric
constant and narrow band gap which make them suitable for various
technological applications. PbX have been widely used for infrared detection
and lasing devices [1-3]. They are also applicable as thermoelectric materials
[4-6], window coatings [7] and in solar-energy panels [8]. Unlike other
semiconductors, band gaps of PbX increase with temperature and decrease with
pressure [9-10]. Because of their technological applications and unique
properties, study of electronic and optical properties of PbX has received
increased attention of researchers. The electronic and optical properties of PbX
has been studied theoretically as well as experimentally by the number of
workers [11- 28]. Mitchell and Wallis [11] have studied the band structure of
PbX using tight-binding (TB) method. Lin and Kleinman [12] have developed
a new pseudopotential calculation containing all important relativistic effects
including spin-orbit interactions. S. Rabii [13] has calculated the energy band
structure of PbS and PbSe using APW method. The electronic energy band
structures of PbTe, SnTe and GeTe have calculated including spin-orbit
interactions by Tung and Cohen [14]. The electronic band structures of PbS,
PbSe and PbTe have been reported by Overhof and Rossler [15] using the
relativistic Green’s function method. Kohn et al [16] have investigated
electronic band structure and optical properties of PbS, PbSe and PbTe using
the techniques of wavelength-modulation spectroscopy. Wei and Zunger [17]
performed the band structure calculation using general-potential linearized
augmented plane-wave (LAPW) method within LDA. Delin et al [18] has
reported ab-initio calculations of the optical properties of lead chalcogenides
PbX using relativistic FP-LMTO method. Lach-hab et al [19] has determined
the electronic band structure and elastic constants of lead chalcogenides using
LAPW method within LDA and GGA. Rached et al [20] has calculated energy
Chapter 4

gaps and optical properties under pressure. The study of electronic and lattice
dynamics properties of the lead chalcogenides have been performed by Zhang
et al [21] using DFT. Santoni et al [22] has investigated band structure of lead
sulphide using angle-resolved photo emission, with synchrotron radiation in the
photon energy range 25-95 eV as excitation source. Romero et al [23] has
performed experimental studies and ab-initio calculations on lattice properties
of PbX including spin-orbit effects. Nimtz and Schlicht [24] have studied
narrow band gaps of lead salts experimentally. Nabi et al [25] has observed
dependence of the energy gaps of PbX on hydrostatic pressure at symmetry
points in the Brillouin zone using the self consistent scalar-relativistic FP-
LAPW method. The study of electronic properties of PbX has been reported by
Hummer et al [26] using FP-LAPW and PAW calculations. Svane et al [27] has
calculated electronic band structures of PbX with the quasi particle self-
consistent GW (QSGW) approach with spin-orbit coupling. Labidi et al [28]
has investigated structural, electronic, optical and thermodynamic properties of
PbS, SrS and their ternary alloys using FP-LAPW method.
As the above review suggests, a number of studies have been reported
on electronic and optical properties for PbX using various methods but the
pressure dependent band structure, Compton profile and equal-valence-
electron-density profile have been hardly studied. To my knowledge, there is no
theoretical study on pressure dependant electronic and optical properties of
PbX compounds using LCAO technique. The aim of this chapter is to explore
the dependence of the electronic and optical properties of PbX on hydrostatic
pressure, by employing the LCAO method. This chapter is organized as
follows: In section 4.2, the computational details are described. The result and
discussion are presented in section 4.3. Conclusion of work is summarized in
section 4.4.
4.2 Computational details
The study of electronic and optical properties of PbX have been made
using the ab-initio LCAO method embodied in the CRYSTAL06 code [29]. In
this method, each crystalline orbital ψ i(r,k) is a linear combination of Bloch
Chapter 4

functions φμ(r,k) defined in terms of local functions φ μ(r), normally referred as


atomic orbitals. The local functions have been expressed as linear combination
of certain number of individually normalized Gaussian-type functions. For Pb,
S, Se and Te, the local functions have been constructed from the Gaussian type
basis sets [30]. The exchange and correlation have been treated under the GGA.
The correlation functional proposed by PBE [31] has been applied while
exchange functional has been considered by applying the Becke’s ansatz [32].
The self-consistent calculations have performed considering 29 k points in the
irreducible Brillouin zone with sufficient tolerances. To achieve self-
consistency, 70% mixing of successive cycles has been considered and self
consistency has been achieved within 10 cycles.
It has been well established that valence EMD is an important ground
state property. In the independent particle model, the momentum density n(p) is
given by [33, 34]
2
n ( p )  ��y i (r ) exp(ip.r ) dr (4.1)
i

where n(p) is the three dimensional momentum density and ψ(r) represents the
electron wave function. The summation is all over the occupied states. The
Compton profile can be derived from the ground state momentum density n(p)
as
� �
J ( p z )  � �n ( p ) dp x dp y (4.2)
� �

The spherically averaged Compton profile is determined by the


averaged momentum density as
�
J ( p z )  2p ��n ( p) �
pdp (4.3)
pz

4.3 Results and Discussion


4.3.1 Electronic properties
The equilibrium lattice constants calculated by LCAO method have
been used to investigate the electronic band structures of PbX. The different
symmetry points W (0.5, 0.25, 0.75), L (0.5, 0.5, 0.5), Γ (0.0, 0.0, 0.0), X (0.5,
Chapter 4

0.0, 0.0), W (0.5, 0.25, 0.75) and K (0.375, 0.375, 0.75) have been considered
in the Brillouin zone (BZ). The band structures of PbS, PbSe and PbTe have
been shown in Figures 4.1-4.3 respectively. From Figures, it is visible that for
these compounds, valence band maximum (VBM) and conduction band
minimum (CBM) occur at the L point of Brillouin zone which indicates that
PbX have direct band gap along L direction in stable phase. The calculated
direct energy gaps (L-L) of PbX along with previously reported experimental
and theoretical results have been mentioned in Table 4.1.
For visualizing the variation of energy band gap with hydrostatic
pressure, energy structure of PbS in B1 phase at different pressure have been
investigated (Figures 4.4-4.7). From figures, it is clearly visible that PbS has
direct band gap (L-L) at all different pressures. Table 4.2 contains values of
band gap of PbS at different positive and negative pressures. The effect of
pressure on energy band gap of PbS in B1 phase is shown in Figure 4.8. A
similar variation of energy band gap with pressure has been presented by Nabi
et al [25]. Density of state of PbS, PbSe and PbTe have also been presented in
Figures 4.9-4.11 respectively.
To study the directional features in the electron momentum density,
anisotropies are studied for PbS. The unconvoluted directional and spherically
averaged theoretical Compton profiles, J(pz), for PbS at different pressures i.e.
0, 5 and 10 GPa are calculated. The anisotropies ([111]-[110], [111]-[100] and
[110]-[100]) in the directional Compton profiles for PbS at different hydrostatic
pressures 0, 5 and 10 GPa are plotted in Figure 4.12 (a)-(c). This figure shows
that at zero pressure, [111]-[110] anisotropy is negative and the anisotropy
between the [110] and [100] directions is maximum at pz=0.0 a.u.
Chapter 4

10

Energy (eV)

0 EF

-5

-10

-15
W L  X W K

Figure 4.1 Energy band structure B1 phase of PbS at pressure (P) = 0 GPa.
Chapter 4

10

0 EF
Energy (eV)

-5

-10

-15
W L  X W K

Figure 4.2 Energy band structure B1 phase of PbSe at pressure (P) = 0 GPa.
Chapter 4

10

0 EF
Energy (eV)

-5

-10

-15
W L  X W K

Figure 4.3 Energy band structure B1 phase of PbTe at pressure (P) = 0 GPa.
Chapter 4

Table 4.1
The calculated direct band gaps (in units of eV) of PbX along with
previous data.

Present Experimental Other calculations


PbS 0.359 0.29 [24] 0.26 [25],
0.31 [26],
0.31 [27],
0.498 [28]
PbSe 0.185 0.17 [24] 0.16 [25],
0.18 [26],
0.21 [27]
PbTe 0.261 0.19 [24] 0.17 [25],
0.25 [26],
0.29 [27]
Chapter 4

10

0
Energy (eV)

EF

-5

-10

-15
W L  X W K

Figure 4.4 Energy band structure B1 phase of PbS at pressure (P) = -2 GPa.
Chapter 4

10

0
Energy (eV)

EF

-5

-10

-15
W L  X W K

Figure 4.5 Energy band structure B1 phase of PbS at pressure (P) = -1 GPa.
Chapter 4

10

5
Energy (eV)

0 EF

-5

-10

-15
W L  X W K

Figure 4.6 Energy band structure B1 phase of PbS at pressure (P) = 1 GPa.
Chapter 4

10

5
Energy (eV)

0 EF

-5

-10

-15
W L  X W K

Figure 4.7 Energy band structure B1 phase of PbS at pressure (P) = 2 GPa.
Chapter 4

Table 4.2
Dependence of the band gap on positive and negative pressures for B1
phase of PbS.

Pressure (GPa) Lattice constant (Å) Direct gap (L-L) (eV)


-2 5.95 0.470
-1 5.91 0.394
0 5.89 0.359
1 5.86 0.317
2 5.83 0.258
Chapter 4

75 PbS
EF

50

25

0
75 S
50
DOS (arb. units.)

25

0
75
Pb

50

25

0
-15 -10 -5 0 5 10
Energy (eV)

Figure 4.8 Density of states of B1 phase of PbS.


Chapter 4

EF PbSe
90

60

30

0
90 Se

60
DOS (arb. units.)

30

0
Pb
90

60

30

0
-15 -10 -5 0 5 10
Energy (eV)

Figure 4.9 Density of states of B1 phase of PbSe.


Chapter 4

EF PbTe
75

50

25

0
Te
75

50
DOS (arb. units.)

25

75
Pb

50

25

0
-15 -10 -5 0 5 10

Energy (eV)

Figure 4.10 Density of states of B1 phase of PbTe.


Chapter 4

0.50

0.45

0.40
Energy gap (eV)

0.35

0.30

0.25

-2 -1 0 1 2
Pressure (GPa)

Figure 4.11 Variation of the energy band gap at (L) point with pressure for
PbS.The solid line shows the linear fit and dots show the calculated values.
Chapter 4

0.6 J111-J110
0.4
(a) P=10 GPa
J111-J100
0.2
J110-J100
0.0
-0.2
-0.4
-0.6
0.6
0.4 (b) P= 5 GPa
0.2
 J (e/a.u.)

0.0
-0.2
-0.4
-0.6
0.6
0.4 (c) P= 0 GPa
0.2
0.0
-0.2
-0.4
-0.6
0 1 2 3
Pz (a.u.)

Figure 4.12 Compton profile anisotropies obtained from unconvoluted


directional Compton profiles for B1phase of PbS (a) P=10 GPa, (b) P=5 GPa,
(c) P= 0 GPa using LCAO method.
Chapter 4

As pressure increases, [111]-[110] anisotropy becomes more negative


and [110]-[100] becomes more positive. The anisotropy is hardly visible
beyond 1.5 a.u.
The nature of bonding in isovalent and isostructural compounds can be
understood by the EVED profiles [35]. The theoretical EVED profiles for PbX
have been calculated by DFT-PBE valence profiles by normalizing the valence
electron profiles to 5.0 electrons and scaling the resulting profiles by the Fermi
momentum (pF). For PbS, PbSe and PbTe, pF turned out to be 0.950, 0.9226 and
0.8669 a.u., respectively, by using the expression (3π2n) 1/3, where n is the
valence electron density.
The nature of bonding in PbS, PbSe and PbTe are compared on the basis
of EVED profiles in Figure 4.13.The EVED profile corresponding to PbTe is
larger around the low momentum region compared with other compounds. As a
larger value around the low momentum region is attributed to a greater
covalent character, it shows that PbTe is more covalent than PbSe and PbS. The
variation in the nature of bonding in PbS under pressure is also studied on the
basis of EVED profiles in Figure 4.14.
4.3.2 Optical properties
The optical dielectric constants of PbX are calculated and reported in
Table 4.3 which shows that the trend of dielectric constants for the lead
chalcogenides is PbS < PbSe < PbTe. To investigate the variation of static
dielectric constant with pressure, dielectric constant of PbS are calculated at
different pressures (Table 4.4). The pressure dependency of dielectric constant
for PbS is shown in Figure 4.15. From this Figure, it is observed that the static
dielectric constant increases with increasing pressure.
Chapter 4

PbS
6 PbSe
PbTe

4
J (p z)*p F

0
0 1 2 3 4 5
pz/pF

Figure 4.13 The equal-valence-electron-density (EVED) profiles for PbS, PbSe


and PbTe. All profiles are normalized to 5.0 electrons.
Chapter 4

6
0 GPa
5 GPa
5 10 GPa

4
J (p z )*p F

0
0 1 2 3
pz/pF

Figure 4.14 The equal-valence-electron-density (EVED) profiles for PbS at


different pressures. All profiles are normalized to 5.0 electrons.
Chapter 4

Table 4.3
The dielectric constant on negative and positive pressures for B1 phase of
PbX.

Present Other calculations


PbS 15.292 17[36], 17.4[37]
PbSe 19.678 23[36]
PbTe 25.582 33 [36]
Chapter 4

Table 4.4
Dependence of the dielectric constant on negative and positive pressures
for B1 phase of PbS.

Pressure (GPa) Dielectric constant


-2 14.439
-1 14.786
0 15.292
1 15.560
2 16.121
Chapter 4

16.2

16.0

15.8

15.6
Dielectric constant

15.4

15.2

15.0

14.8

14.6

14.4

-2 -1 0 1 2
Pressure (GPa)

Figure 4.15 Variation of the dielectric constant with pressure for PbS. The solid
line shows the linear fit and dots show the calculated values.
Chapter 4

4.4 Conclusions

The electronic and optical properties of PbX (X=S, Se and Te)


compounds are reported in this chapter. The main results are summarized are
follow:-
(i) The PbX compounds have direct band gap along the L direction of Brillouin
zone.
(ii) The band gap of PbS decreases with increasing pressure.
(iii) PbTe has more covalent nature as compared to PbS and PbSe.
(iv) The covalent nature of PbS increases under pressure.
(v) The trend of optical dielectric constant in the lead chalcogenides is
PbS < PbSe < PbTe.
(vi) The static dielectric constant of PbS increases with increasing pressure.
Chapter 4

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lead chalcogenides from first principles,Phys. Rev. B 75 (2007) 195211.

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Chapter 4

Chapter 5

Structural and electronic properties of doped


lead-chalcogenides
Chapter 4

5.1 Introduction

The lead chalcogenides (PbX, X=S, Se and Te) are a special class of IV-
VI narrow band gap (0.2-0.4 eV) semiconductors. Due to its unique structural
and electronics properties, these materials are of great interest of research from
past few decades. Many experimental and theoretical studies have been
performed on their structural and electronic properties [1-6].
All these theoretical calculations identified a direct band gap at L point
of Brillouin zone (BZ) for all lead chalcogenides. These materials are stable in
the rocksalt structure at ambient temperature and pressure.
It is well known that, by introducing foreign atom into a semiconductor,
structural and electronic properties can be changed. The doping process can
significantly affect the physical properties of lead chalcogenides, and it
provides an easy way of changing the grain size and thus, its emission and
absorption wavelength, or optical band gap of these materials.
To learn more about the nature of these materials, few experimental and
theoretical studies were performed on structural and electronic properties of
doped lead chalcogenides. Moreno et al [7] reported the modification of
structural, optical and electrical properties of PbS thin film due to doping of
Ni2+. They presented the growth of nanocrystalline Ni 2+ doped PbS thin films
by chemical bath deposition onto glass. They reported, with the concentration
of Ni2+ in PbS thin film, the grain size of sample shifts from 36 nm to the range
3.5-5 nm and the energy band gap shifts from 0.4 eV to the range 2.1-3.8 eV.
Das and Kumar [8] presented the deposition of nanocrystalline Sn doped
PbS thin films on suitable cleaned glass substrate at constant room temperature,
using the chemical bath deposition technique. They examined the effect of
concentration of Sn in PbS thin film on their structural and optical properties.
They reported crystallite size increases and optical band gap reduces with
increasing doping concentration of Sn in pure PbS.
The structural, optical and electrical properties of cadmium-doped PbSe
thin films were studied by Khan et al [9]. They prepared (PbSe) 100-xCdx thin
Chapter 4

films of thickness 3000 Å with variable concentration of Cd (x=5,10,15 and 20)


by thermal evaporation on glass substrates at room temperature at base pressure
of 10-6 Torr. They reported the optical band gap decreases with increasing
doping concentration of Cd in pure PbS.
Khanlary and Salavati [10] described the physical vapor deposition of
tin-doped PbSe thin films on SiO2 glass. They reported the effects of the
concentration of Sn in PbS thin film on their structural and optical parameters.
Kumar et al [11] deposited the high quality polycrystalline thin films of
PbS1-xSex with variable composition (0≤x≤1) on ultra clean glass substrates by
vacuum evaporation technique and examined structural, electrical and optical
properties of PbS1-xSex. Schoolar et al [12] has prepared multispectral PbS 1-xSex
photovoltaic infrared detectors from 1–10 μm by depositing Pb Schottky
barrier contacts on layered structures of the lead salt alloy semiconductors
epitaxially grown on BaF2 substrates.
Theoretically, Zaoui et al [13] and Kacimi et al [14] have reported
structural and electronic properties of PbS1-xTex and PbSe1-xTex alloys by means
of the hybrid FP-LAPW+lo method.
Recently, Boukhris et al [15] also investigated structural, electronic and
thermodynamic properties of PbS1-xSex, PbS1-xTex and PbSe1-xTex ternary alloys
by using the FP-LAPW.
In the present work, the structural and electronic properties of ternary
alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex (x=0.0, 0.25, 0.50, 0.75, 1.0) have
been reported using LCAO method. These properties are studied in terms of
lattice constant, bulk modulus, pressure derivative of bulk modulus and energy
band gap. Variation in lattice constant, bulk modulus and in energy band gap as
a function of concentration i.e. x for PbS1-xSex, PbS1-xTex and PbSe1-xTex alloys
are estimated.
An outline of this chapter is as follows: A brief description of
computational details is given in Section 5.2 and the results are discussed in
Section 5.3. The last Section 5.4 summarizes the results of this investigation.
Chapter 4

5.2 Computational details

The ab-initio LCAO method embodied in CRYSTAL06 code [16] have


been used to study the structural and electronic properties of PbS 1-xSex, PbS1-
x Tex and PbSe1-xTex alloys. In this method, each crystalline orbital ψ i(r,k) is a
linear combination of Bloch functions φμ(r,k). The Bloch functions are defined
in terms of local functions φμ(r), normally referred as atomic orbitals. There
are a few fundamental schemes exist for constructing the Hamiltonian for the
periodic solids, in which HF approximation [17] and the DFT [18] are the well-
known approaches among these schemes. Under the DFT, a number of
functional exist to treat exchange and correlation. In the present work, the local
functions for Pb, S, Se and Te were constructed from the Gaussian type basis
sets [19]. The Kohn-Sham Hamiltonian was constructed while considering the
exchange scheme of Becke [20] and correlation scheme of PBE [21].
In the present work, the structural and electronic properties of ternary
alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex (x= 0.0, 0.25, 0.50, 0.75, 1.0) were
analyzed for rocksalt structure. The ternary alloys PbS 1-xSex, PbS1-xTex and
PbSe1-xTex were simulated by substituting the S, Se and Te in periodically
repeated supercells.
In order to calculate the lattice constant of PbS 1-xSex, PbS1-xTex and
PbSe1-xTex (x = 0.0, 0.25, 0.50, 0.75, 1.0), the structural optimization was
performed by calculating the total energy for different volumes around the
equilibrium cell volume V0 of alloys. Then calculated lattice constants were
used to investigate the electronic properties. The self-consistent calculations
were performed considering 29k and 80k points for binary and ternary alloys,
respectively, in the irreducible Brillouin zone with tight tolerances. To achieve
self-consistency 70% mixing of successive cycles were considered and
achieved within 10 cycles.
5.3 Results and Discussion
5.3.1 Structural properties
Chapter 4

The ground state properties such as the lattice constants (a), bulk
modulus (B), pressure derivative of bulk modulus (B’) were computed by
fitting the total energy versus volume according to the third order Birch-
Murnaghan equation of state [22,23]. The calculated lattice constants and bulk
modulus for B1 phase of the binary compounds (PbS, PbSe and PbTe) and their
alloys (PbS1-xSex, PbS1-xTex and PbSe1-xTex) are listed in Tables 5.1-5.3, which
also contain the previous theoretical and experimental results. The calculated
structural parameters are in good agreement with the previous results.
To the best of my knowledge, no experimental data are available for
structural parameters of the ternary alloys (PbS 1-xSex, PbS1-xTex and PbSe1-xTex).
Hence, our calculated results can serve as a prediction for future research.
Figures 5.1(a)-(c) show the variation of the calculated lattice constant versus
concentration for the alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex respectively.
From these Figures, it is clear that the values of calculated lattice constant vary
with the concentration of doping in the similar trend with the values of Vegard 's
law [24] with small deviation.
Figures 5.2(a)-(c) show the variation of the calculated bulk modulus
versus concentration for the alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex
respectively.

5.3.2 Electronic properties


In order to compute the energy band gap, calculated equilibrium lattice
constant are used. The electronic band structures for B1 phase of the ternary
alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex (x=0.25, 0.50 and 0.75) are shown in
Figures 5.3-5.11 respectively. In the ternary alloys PbS 1-xSex, PbS1-xTex and
PbSe1-xTex with concentration of doping x=0.25 and 0.75, the valence band
maximum (VBM) and conduction band minimum (CBM) occur at the L point
of Brillouin zone (BZ) but for x=0.50, direct band gaps are observed along the
highly symmetric direction (i.e Γ). The calculated and available previous
results of the energy band gaps are given in Table 5.4.
Chapter 4

Table 5.1

x= 0 x = 0.25 x = 0.50 x = 0.75 x= 1


a (Å)
Present 5.89 5.92 6.028 6.04 6.08
Vegards Law 5.89 5.93 5.98 6.03 6.08
Experiment 5.940[1], - - - 6.133[1],
5.936[2], 6.124[2],
5.929[3] 6.117[3]

Other 6.000[4], 6.069[14], 6.122[14], 6.174[14], 6.211[4],


Calculations 6.006[5], 6.073[15] 6.128[15] 6.179[15] 6.214[5],
6.012[6], 6.226[6],
6.012[14], 6.565[14],
6.010[15] 6.210[15]
B0
(GPa)
Present 67.9 67.6 67.2 67.1 66.9
Experiment 62.8[2], - - - 54.1[2],
62.2[3] 54.1[3]
Other 54.63[4], 50.8[14], 49.7[14], 48.2[14], 48.27[4],
calculations 56.0[5], 49.21[15] 47.46[15] 46.78[15] 49.5[5],
52[6], 44.5[6],
53.3[14], 49.1[14],
53.38[15] 49.18[15]

B0'
Present 3.9 4.2 4.3 4.1 4
Experiment - - - - -
Other 4.10[4], - - - 4.35[4],
calculations 3.6[5] 3.8[5]

Calculated lattice parameter (a), bulk modulus (B 0) and its pressure


derivatives (B0') for PbS1-xSex (x=0, 0.25, 0.5, 0.75 and 1.0).
Chapter 4

Table 5.2

x= 0 x = 0.25 x = 0.50 x = 0.75 x= 1


a (Å)
Present 5.89 6.0 6.15 6.25 6.462
Vegards 5.89 6.033 6.176 6.319 6.462
Law
Experiment 5.940[1], - - - 6.458[1],
5.936[2], 6.462[2],
5.929[3] 6.443[3]
Other 6.000[4], 6.188[15] 6.325[15] 6.450[15] 6.554[4],
calculations 6.006[5], 6.566[5],
6.012[6], 6.582[6],
6.010[15] 6.560[15]
B0
(GPa)
Present 67.9 63 57.5 53.4 49
Experiment 62.8[2], - - - 39.8[2],
62.2[3] 41.1[3]
Other 54.63[4], 45.744[15] 44.368[15] 39.462[15] 39.95[4],
calculations 56.0[5], 41.0[5],
52[6], 37.5[6],
53.384[15] 38.406[15]
B0'
Present 3.9 4.1 4 3.9 4.1
Experiment - - - - -
Other 4.10[4], - - - 4.32[4],
calculations 3.6[5] 4.6[5]
Calculated lattice parameter (a), bulk modulus (B 0) and its pressure
derivatives (B0') for PbS1-xTex (x=0, 0.25, 0.5,0.75 and 1.0).
Chapter 4

Table 5.3
Calculated lattice parameter (a), bulk modulus (B 0) and its pressure
derivatives (B0') for PbSe1-xTex (x=0, 0.25, 0.5, 0.75 and 1.0).

x= 0 x = 0.25 x = 0.50 x = 0.75 x= 1


a (Å)
Present 6.08 6.25 6.35 6.36 6.462
Vegards 6.08 6.175 6.271 6.366 6.462
Law
Experiment 6.133[1], - - - 6.458 [1],
6.124[2], 6.462[2],
6.117[3] 6.443[3]

Other 6.211[4], 6.320[15] 6.406[15] 6.487[15] 6.554[4],


calculations 6.214[5], 6.566[5],
6.226[6], 6.582[6],
6.210[15] 6.560[15]
B0
(GPa)
Present 66.9 60.3 57.8 52.5 49
Experiment 54.1[2], - - - 39.8[2],
54.1[3] 41.1[3]
Other 48.27[4], 44.489[15] 41.101[15] 37.791[15] 39.95[4],
calculations 49.5[5], 41.0[5],
44.5[6], 37.5[6],
49.187[15] 38.406[15]
B0'
Present 4 4.3 3.9 4.2 3.8
Experiment - - - - -
Other 4.35[4], - - - 4.32[4],
calculations 3.8[5] 4.6[5]
Chapter 4

6.10

(a)
LCAO
Vegard's Law
6.05

Lattice constant (Å)


6.00

5.95

5.90

5.85
0.0 0.2 0.4 0.6 0.8 1.0
Composition x

6.5 (b)
LCAO
Vegard's Law
6.4
Lattice constant (Å)

6.3

6.2

6.1

6.0

5.9

5.8
0.0 0.2 0.4 0.6 0.8 1.0

Composition x

6.50
(c)
6.45
LCAO
6.40 Vegard's Law
Lattice constant (Å)

6.35

6.30

6.25

6.20

6.15

6.10

6.05

0.0 0.2 0.4 0.6 0.8 1.0

Composition x
Chapter 4

Figure 5.1 Calculated lattice constants as a function of composition for


(a) PbS1-xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys.

68.0
(a)
67.8

67.6

Bo(GPa)
67.4

67.2

67.0

66.8
0.0 0.2 0.4 0.6 0.8 1.0

Composition (x)

70

(b)

65

60
Bo(GPa)

55

50

45
0.0 0.2 0.4 0.6 0.8 1.0
Composition (x)

68
(c)
66

64

62

60
Bo(GPa)

58

56

54

52

50

48

0.0 0.2 0.4 0.6 0.8 1.0

Composition (x)
Chapter 4

Figure 5.2 Calculated bulk modulus as a function of composition for (a) PbS1-
xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys.

2
Energy (eV)

0 Ef

-2

-4

W L  X W K

Figure 5.3 Energy band structure of B1 phase of PbS0.75Se0.25.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.4 Energy band structure of B1 phase of PbS0.50Se0.50.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.5 Energy band structure of B1 phase of PbS0.25Se0.75.


Chapter 4

2
Energy (eV)

0
EF

-2

-4

W L  X W K

Figure 5.6 Energy band structure of B1 phase of PbS0.75Te0.25.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.7 Energy band structure of B1 phase of PbS0.50Te0.50.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.8 Energy band structure of B1 phase of PbS0.25Te0.75.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.9 Energy band structure of B1 phase of PbSe0.75Te0.25.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.10 Energy band structure of B1 phase of PbSe0.50Te0.50.


Chapter 4

2
Energy (eV)

0 EF

-2

-4

W L  X W K

Figure 5.11 Energy band structure of B1 phase of PbSe0.25Te0.75.


Chapter 4

Table 5.4
Energy band gap (in eV) for PbS 1-xSex, PbS1-xTex and PbSe1-xTex (x=0, 0.25,
0.5, 0.75 and 1.0).

x= 0 x = 0.25 x = 0.50 x = 0.75 x= 1


PbS1-xSex
Present 0.36 0.2 1.21 0.1 0.18
Experiment 0.29[25] - - - 0.17[25]
Other 0.496[15], 0.427[15], 0.342[15], 0.329[15] 0.425[15],
Calculations 0.26[26], 0.340[28], 0.737[28], 0.16[26],
0.29[27], 0.295[29] 0.730[28] 0.17[27]
0.380[28]
PbS1-xTex
Present 0.36 0.11 1.20 0.2 0.26
Experiment 0.29[25] - - - 0.19[25]
Other 0.496[15], 0.256[15] 0.161[15] 0.136[15] 0.833[15],
calculations 0.26[26], 0.17[26],
0.29[27] 0.19[27]

PbSe1-xTex
Present 0.18 0.13 1.18 0.23 0.26
Experiment 0.17[25] - - - 0.19[25]
Other 0.425[15], 0.329[15] 0.342[15] 0.427[15] 0.496[15]
calculations 0.16[26], 0.17[26],
0.17[27] 0.19[27]
Chapter 4

1.4

(a)
1.2

1.0

0.8

Eg (eV)
0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Composition x

1.2 (b)

1.0

0.8
Eg (eV)

0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Composition x

1.2 (c)

1.0

0.8
Eg (eV)

0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Composition x

Figure 5.12 Calculated Energy band gap as a function of composition for


(a) PbS1-xSex,(b) PbS1-xTex and (c) PbSe1-xTex alloys.
Chapter 4

For better visualizing, the variation of the energy band gap with the
concentration of doping for the alloys PbS 1-xSex, PbS1-xTex and PbSe1-xTex is
presented in Figure 5.12(a)-(c) respectively. The Figure 5.12(a)-(c) depict the
energy band gap of the alloys PbS 1-xSex, PbS1-xTex and PbSe1-xTex vary in similar
manner with concentration of doping.
5.4 Conclusions
In summary, the first-principles LCAO calculations are used to study the
structural and electronic properties of the ternary alloys PbS 1-xSex, PbS1-xTex
and PbSe1-xTex (x=0.0, 0.25, 0.50, 0.75, 1.0). The main results are listed as
following:
(i) With the concentration of doping, the lattice constant increases whereas the
bulk modulus decreases.
(ii) The calculated structural parameters for all the ternary alloys PbS1-xSex,
PbS1-xTex and PbSe1-xTex are in agreement with previous results.

(iii) In the ternary alloys PbS1-xSex, PbS1-xTex and PbSe1-xTex with concentration
of doping x=0.25 and 0.75, direct band gaps are observed along the L direction
but for x=0.50, direct band gaps are observed along the Γ direction.

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Chapter 4

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Crystalline Solids (Lecture Notes in Chemistry vol 48) (Heidelberg: Springer),
(1988).

[18] R. Dovesi, R. Orlando, C. Roetti, C. Pisani and V.R. Saunders, The Periodic
Hartree-Fock Method and Its Implementation in the Crystal Code, Phys. Status Solidi
b 217 (2000) 63.

[19] (www.tcm.phy.cam.ac.uk/).

[20] A.D. Becke, Density‐functional thermochemistry, III.The role of exact exchange,


J. Chem. Phys. 98 (1993) 5648.

[21] J.P. Perdew, K. Burke and M. Ernzerhof, Generalized Gradient Approximation


Made Simple, Phys. Rev. Lett. 77 (1996) 3865.

[22] F. Brich, Finite elastic strain of cubic crystals, J. Geophys. Res. 83 (1978) 1257.

[23] J.P. Poirer, Introduction to the Physics of Earth’s Interior, Cambridge University
Press, Cambridge, 27 (1992) 193.

[24] L. Vegard, Die Konstitution der Mischkristalle und die Raumfüllung der Atome,
Z. Phys. 5 (1921) 517.

[25] G. Nimtz and B. Schlicht, Narrow-gap Semiconductors, Springer, New York,


1985.

[26] Z. Nabi, B. Abbar, S. Mecabin, A. Khalfi and N. Amrane, Pressure dependence


of band gaps in PbS, PbSe and PbTe, Comput. Mater. Sci. 18 (2000) 127.

[27] S.H. Wei and A. Zunger, Electronic and structural anomalies in lead
chalcogenides, Phys. Rev. B 55 (1997) 13605.

[28] M. Lach-hab, A.D. Papaconstantopoulos and J.M. Mehl, Electronic structure


calculations of lead chalcogenides PbS, PbSe, PbTe, J. Phys. Chem. Solids 63 (2002)
833.
Chapter 4

[29] E.A. Albanesi, C.M.I. Okoye, C.O. Rodriguez, E.L. Peltzer, Y. Blanca and A.D.
Petukhov, Electronic structure, structural properties, and dielectric functions of IV-VI
semiconductors: PbSe and PbTe, Phys. Rev. B 61 (2000) 16589.

Chapter 6

Synthesis and characterization of PbS


micro- and nano-crystals
Chapter 4

6.1 Introduction
The luminescence nature of crystals depends on their shapes and sizes
[1]. Because of the strong relation between shapes and properties, one of the
desired goals in material science is to control the morphology of
semiconductors. It is technologically important to study the factors on which
morphology of semiconductors depends. Lead sulfide is a IV-VI
semiconductor with a cubic rocksalt structure. It has attracted considerable
Chapter 4

attention due to its narrow band gap (Eg = 0.41eV) [2,3] and large excitation
Bohr radius (18 nm) [4] and is widely used in various of fields such as sensors
[5], photography [6], IR detectors [7], thermo photovoltaic energy converters
[8] and solar cells [9] etc.
Due to large excitation Bohr radius, size quantization effects are to be
clearly visible even for relatively large particles or crystals [10]. PbS is an
interesting system for studying the effects of size confinements. Recently
many methods have been developed to synthesis PbS nanomaterials with
different morphologies.
Ni et al [11] reported PbS micron crystals with a flower-like structure
via a simple aqueous-phase route under microwave irradiation, employing
(CH3COO)2Pb, Na2S2O3 and H2O as the staring materials. Zhou et al [12]
synthesized well-defined single-crystalline PbS nano- and micro structures
including star-shaped dendrites and truncated nano cubes in high yield by a
simple solution route. They observed that different morphologies of crystal
can be obtained by programming growth parameters such as the molar ratio,
the initial reaction temperature and period of reaction. Zhang et al [13]
developed the pure PbS micro crystallites with irregular polyhedral, cubic and
fish bone-, star- and flower-like morphologies just via solvothermal
decomposition of the lead diethyldithiocarbamate (Pb-DDTC) in three
different solvents including ethanol, ethylene glycol and ethylenediamine at
150-180 °C for 12 h. Wang et al [14] prepared various PbS crystals having
different structures like cubic, truncated octahedral, flower-shaped, cross-
shaped structure by a reflux process using CTAB as a surfactant. They
investigated parameters affecting the morphology of PbS and found that
various PbS structures can be obtained by changing the sulphur and lead
source, the solvent or the surfactant. Qiu et al [15] demonstrated a new, facile
and environment friendly electro-chemical deposition process of PbS crystals
with the capacity of systematically tuned morphologies. They reported, with
the change of concentration of precursor PbCl 2, PbS crystal shows continuous
shape change from octahedral to star-like, then to football-like, and finally to
Chapter 4

cubic morphology. Sashchiuk et al [16] prepared PbS nanocrystals embedded


in amorphous zirconia sol-gel films of different PbS mole concentrations (5-
30%) at temperature, ranging from 200 °C to 350 °C. They observed that the
size of PbS nanocrystals increases with an increase of synthesis temperature
and PbS mole concentration. Wang et al [17] established a novel
sonochemical method for the preparation of PbS nanocrystals in oil-in-water
microemulsions. Vu et al [18] synthesized PbS nanocrystals via sonochemical
and sonoelectrochemical methods.
In spite of all these researches, it is still a challenge to develop a novel
and simple approach for the large yield of nano-materials with desired
morphology. In the present work, the synthesis of PbS micro and nanocrystals
with different morphologies via hydrothermal and microwave approaches
have been considered. The effect of hydrothermal reaction time on the
morphology of PbS crystals has also been investigated.
This chapter is organized as follows: In section 6.2 the experimental
detail is described. The results are discussed in section 6.3. A conclusion of
work is given in section 6.4.
6.2 Experimental details
6.2.1 Synthesis of PbS crystals
To synthesize PbS crystals via hydrothermal process, 0.036 mol lead
acetate, 0.142 mol thiourea and 8.57 mmol CTAB were dissolved into 40 mL,
20 mL and 20 mL deionized water, respectively. Then thiourea was added
with lead acetate dropwise under constant stirring condition at room
temperature followed by CTAB solutions.
The mixture was transferred to 100 mL Teflon lined stainless steel auto
clave. After sealing, the auto clave was maintained to 180 °C for different
times (2 h, 4 h, 6 h and 12 h) and cooled to room temperature naturally.
In the microwave method, the mixture was transferred to microwave
vessel and irradiated under microwave radiations for 5 min.
The next reaction treatment procedure was the same for both methods.
After cooling to room temperature, the precipitates were filtered off and
Chapter 4

washed with distilled water and absolute ethanol. After drying in air at 60 °C
for 6 h, the final products were collected for characterizations.
6.2.2 Characterizations
The X-ray powder diffraction (XRD) pattern of the products were
recorded by employing a Bruker D8 advance X-Ray diffractometer with Cu
Kα radiation (λ =1.54 Ǻ). The morphology and size of the products were
examined by a scanning electron microscope (SEM) using ZEISS, EVO 18.
The absorption spectra were recorded using Perkin Elmer Lambda 750 UV-
VIS-NIR spectrometer in the wavelength range of 200-800 nm at room
temperature. The Raman spectra were recorded with Deltanu advance Raman
spectrometer using a 532 nm laser beam. To investigate the chemical structure
of PbS micro/nanocrystals, FTIR spectra was taken on Agilent Carry 600
Fourier transform infrared spectrometer. Photoluminescence (PL)
measurements were carried out on a Perkin Elmer LS45 fluorescence
spectrophotometer using 335.2 nm excitation wavelength.
6.3 Results and Discussion

6.3.1 XRD analysis


Figures 6.1 and 6.2 show the XRD pattern of PbS crystals prepared by
hydrothermal method (reaction time 2 h) and microwave method (reaction
time 5 min) respectively. The patterns show various diffraction peaks at 2θ
value 25.3°, 30°, 42.5°, 50.7°, 53.12°, 62.36° and 68.2°.
Chapter 4

25000

20000 200

111
Intensity (a.u.)

15000
220

10000
311

5000 222
400 331

0
10 20 30 40 50 60 70

2 (Degree)

Figure 6.1 X-ray diffraction (XRD) pattern of PbS crystal obtained by


hydrothermal process (reaction time 2 h).
Chapter 4

50000

40000

30000
Intensity

20000

10000

0
10 20 30 40 50 60 70

2 (degree)

Figure 6.2 X-ray diffraction (XRD) pattern of PbS crystal obtained by


microwave process.

All these diffraction peaks can be assigned to the reflections from (111),
(200), (220), (311), (222), (400) and (331) planes of the face centre cubic
phase of PbS [19, 20]. No peak of any other phase is detected. The strong and
sharp reflection peaks indicate that the samples are well crystallized. The
particle sizes (d) of the sample can be calculated using the Debye Scherrer
formula [21].
Chapter 4

d = 0.9 λ/β cos θ ( 6.1)

where, λ is the wavelength of the X-Ray used, θ is the angle of reflection and
β is the full width of Bragg peak at half maximum. The mean particle
diameter is calculated to be 91.3 nm from the Scherrer formula.

6.3.2 Morphology analysis


The morphology of synthesized samples have been analyzed using
SEM images. Figure 6.3 displays typical SEM images of the as-obtained PbS
microcrystals. Their images show that the products have been successfully
synthesized in a variety of morphologies and sizes which were influenced by
the hydrothermal times. Several studies have been done on the growth
mechanics of PbS crystals. Wang [22] has recommended that the shape of an
fcc nanocrystal was mainly determined by the ratio of the growth rate in the
<100> to that in the <111> direction. According to Kuange et al. [23], the PbS
grows firstly in the longitudinal direction, <100> direction to form the
nanorod and then grows laterally, the <011> direction, to form the dendrite,
then finally developed into PbS cubes. Ding et al [19] have reported that
<111> and <100> directions are the main and controllable growing directions
of PbS crystals and to form the PbS nanowires, PbS crystals grow along
<100> direction preferentially.
The shape evaluation of PbS crystals observed in our experiment
provides a good example of such processes. Our systematic studies of PbS
crystal growth have demonstrated that the reaction time is a critical factor in
determining the architectural feature of the PbS microcrystal.

(A) (C)
Chapter 4

(B) (D)

Figure 6.3 SEM images of PbS crystals with a reaction time: (A) 2 h, (B) 4 h,
(C) 6 h and (D) 12 h.

Firstly, only irregular shaped PbS crystals have been procured if the
reaction time was 2 h as in Figure 6.3. Secondly, when the reaction time was 4
h, flower like shaped PbS crystals have been produced. When the reaction
time was further prolonged, same flower like shaped crystals have been
produced but the difference has been that the length of the petals at this time
was increased. It confirms that the <100> direction is the preferential
direction in crystal growth of PbS crystals.
By comparing the ratio of intensities of <111> and <200> diffraction
peaks in the XRD pattern of PbS crystal (Figure 6.1), it is clearly shown that
the <100> direction is the preferential direction in crystal growth of PbS
crystals.

6.3.3 Optical Absorption Spectra


Chapter 4

The UV-Vis absorption spectrum of the PbS crystal synthesized via


hydrothermal process with a reaction time 2 h were measured in the range
200-800 nm at room temperature (Figure 6.4). The spectrum gives an intense
absorption centered at 234.71 nm. The optical band gap energy of the samples
can be calculated from the following equation

αhν = k(hν-Eg)n ( 6.2)

where, α is absorption coefficient, hν is the incident photon energy, k is


constant, n = 1/2 for a direct allowed transition. The (αhν) 2 versus hν plot is
shown in Figure 6.5. The energy intercept of a plot of (αhν) 2 versus hν, yields
Eg for a direct allowed transition. From Figure 6.5, the optical band gap
energy of the PbS crystal with a reaction time 2 h is 4.7 eV [20], which shows
a large increment compared with that of bulk PbS (0.41 eV) [1,2]. The
possible reason of a large increment of band gap energy is small effective
mass of carriers in the PbS.

1.2

1.1

1.0

0.9
Absorbance

0.8

0.7

0.6

0.5

0.4

200 300 400 500 600 700 800

Wavelength (nm)
Chapter 4

Figure 6.4 UV-Vis absorption spectrum of the PbS crystal obtained with 2 h
hydrothermal reaction time.

50

40
(ahn )2(eV) 2(cm) -2

30

20

10

2 3 4 5

hn (eV)

Figure 6.5 Plot to calculate the direct band gap of PbS sample prepared with 2
h hydrothermal reaction time.
Chapter 4

Figure 6.6 shows the UV-Vis transmittance spectra of as-prepared PbS


crystals with different reaction time. This figure indicates that as the reaction
time increases from 2 h, a blue shift of transmittance edge is observed; which
results an increment in optical band gap. The increase in the magnitude of the
band gap may be indication of size quantization [20].
Figure 6.7 shows the UV-Vis absorption spectrum of the PbS crystal
prepared via microwave-assisted route. This spectrum has a broad absorption
peak whose center is observed at 248 nm [24]. The band gap of this sample
calculated by Figure 6.8 is 4.9 eV [24].

6.3.4 Raman Spectra


Raman spectra of as-prepared PbS crystals with different hydrothermal
reaction times are shown in Figure 6.9. Raman scattering measurements were
performed using Nd:YAG laser with an excitation wavelength 532 nm.
Although the products were synthesized with different reaction time, the
spectra contain prominent bands at the same wave numbers. All spectra
contain peaks at 334 cm-1, 472 cm-1 and 615 cm-1. The 334 cm-1 peak
corresponds to two phonon process [25, 26]. Those at 472 and 615 cm -1 are
specified as the first and second overtone modes, respectively [26].

6.3.5 FTIR Analysis


Figure 6.10 shows the FTIR transmission spectra of CTAB and CTAB-
capped PbS crystals respectively. FTIR data of pure and surface bound CTAB
molecules are summarized in Table 6.1.
It would be seen from the data summarized in Table-1 that the band
positions of CTAB-capped PbS crystals are same as those of pure CTAB. The
Chapter 4

unchanged frequency positions conclude that there is no intermolecular


interaction between capping agent CTAB and CTAB- capped products.

12 h

6h
Transmittance (%)

4h

2h

200 300 400 500

Wavelength (nm)

Figure 6.6 UV-Vis transmittance spectra of as-prepared PbS crystals with


different reaction time.
Chapter 4

10

6
Absorbance

200 300 400 500 600 700 800

Wavelength (nm)

Figure 6.7 UV-Vis absorption spectrum of the PbS crystal obtained with
microwave route.
Chapter 4

4000

3500

3000

2500
( a h n ) 2(eV) 2(cm) -2

2000

1500

1000

500

-500
2 3 4 5

hn (eV)

Figure 6.8 Plot to calculate the direct band gap of PbS sample prepared under
microwave irradiation.
Chapter 4

12 h

6h
Intensity

4h

2h

200 400 600


-1
Wavenumber (cm )

Figure 6.9 Raman spectra of as-prepared PbS crystals with different


hydrothermal times.
Chapter 4

Figure 6.10 FTIR spectra of CTAB and PbS crystals.


Chapter 4

Table 6.1
FTIR bands position of pure CTAB and PbS crystals with their
assignments [27, 28].

Band position (cm-1)


Pure CTAB PbS crystals

Asymmetric and symmetric 2917, 2849 2848, 2917


streching CH2 vibrations of
alkyl chain
Asymmetric and symmetric 1476, 1396 1474, 1396
C-H scissoring vibrations of
CH3-N+ moiety
C-N+ streching bands 802, 911, 964, 801, 911, 964,
1061, 1141 1061, 1140
Rocking modes of the 720 720
methylene chain
Chapter 4

(A) (B)

(C) (D)

Figure 6.11 Photo luminescence spectra of as-prepared PbS crystals via


hydrothermal reaction with reaction times: (A) 2 h , (B) 4 h, (C) 6 h and (D)
12 h.
Chapter 4

Figure 6.12 Photo luminescence spectrum of PbS crystal obtained by


microwave route.
Chapter 4

6.3.6 Photoluminescence Analysis

Photoluminescence (PL) of the as-obtained PbS products were


characterized using a 335.2 nm excitation wavelength. PL spectra of samples
synthesized via hydrothermal and microwave processes are shown in Figures
6.11 and 6.12 respectively. These samples kept at room temperature were
excited with light of wavelength 335.2 nm using a xenon lamp. In the present
case, the energy used for excitation is less than the optical band gap energy of
samples as calculated by UV-Vis transmittance spectra, so that emission from
defect related trap states is expected to originate instant of emission
corresponding to fundamental recombination. The entire PL spectra shows only
one negative stock shifted emission peak centered at 335 nm, which indicates
that PL comes from PbS products, not from any impurities.
6.4 Conclusions
The conclusions of this chapter are as follows:
(i) The synthesis of PbS crystals via hydrothermal and microwave methods
both are reported.
(ii) The reaction time plays an important role in the evolution of morphology of
PbS crystals.
(iii) The growth rate of PbS crystal along the direction <100> is greater than
that along the direction <111>.
(iv) The microwave method is time saving as compared to hydrothermal
method.
(v) These approaches can also be extended to synthesize other important
semiconductor material with desired morphologies.
Chapter 4

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Chapter 4

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Nanocrystals and Their Assemblies, J. Phys. Chem. B 104 (2000) 1153.

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Chapter 4

Chapter 7

Conclusions and Future scope


Chapter 4

7.1 Conclusions
This thesis mainly deals with two parts: - In the first part of thesis, the
structural, electronic and optical properties of binary and ternary lead-
chalcogenides are studied theoretically using LCAO method as implemented in
the CRYSTAL06 code.. In the second part, synthesis and characterizations of
PbS crystals are reported.
To investigate the structural properties of lead-chalcogenides, lattice
constants, transition pressures, bulk modulus and its pressure derivatives are
investigated. NaCl (B1) phase is the most stable phase for PbX compounds at
ambient conditions. The intermediate phase of PbX between B1 and B2 phases
is observed to be FeB type (B27, Pnma) phase. PbTe is more compressible than
other two compounds. Cohesive energy of PbX decreases under pressure. The
observed transition pressures from stable phase to intermediate phase and from
intermediate to high-pressure phase are in good agreement with the previous
reported experimental and theoretical values.
The electronic properties of lead-chalcogenides are described in terms of
energy bands, momentum density and bonding in theses systems. The PbX
compunds have direct band gap along the L direction of Brillouin zone. The
effect of pressure on electronic properties of PbX is also studied. The energy
band gap of PbX decreases while covalent nature of PbX increases under
pressure. On the basis of EVED profiles, it is observed that PbTe is more
covalent and less ionic than PbS and PbSe. The static dielectric constants of
PbX and their pressure dependency are also reported. The trend of optical
dielectric constant in lead chalcogenides is found as PbS < PbSe < PbTe and
the static dielectric constant of PbX increases with increasing pressure.
The structural and electronic properties of doped lead chalcogenides
PbS1-xSex, PbS1-xTex and PbSe1-xTex (x = 0.0, 0.25, 0.50, 0.75 and 1.0) are
reported. The lattice constants, bulk modulus, its pressure derivatives and
energy band gaps of all these ternary alloys are investigated. The variation in
lattice constant, bulk modulus and band gap with concentration of doping are
Chapter 4

also reported. The results indicate that lattice constant increases while bulk
modulus decreases with the increasing concentration of doping.
The flower shaped PbS micro- and nano-crystals by hydrothermal and
microwave processes are synthesized. To know the effect of reaction time on
morphology of crystal, the hydrothermal process was carried out with
different reaction times. It is found that reaction time plays an important role
in the formation and shapes of products. It was also found that the growth rate
of PbS crystal along the direction <100> is greater than that along the
direction <111>. Microwave method was found to be time saving as
compared with hydrothermal method.
In short, all calculated results are in good agreement with the previous
reported experimental and theoretical results.
Future scope
Some future work based on this thesis can be given as follow:-
a) The theoretical study of structural, electronic and optical
properties of lead-chalcogenides can be made by using other
methods based on augmented plane wave (APW), full-potential
linearized augmented plane-wave (FP-LAPW), Koringa-Kohen-
Rostoker (KKR) and empirical-pseudopotential methods (EPM).
b) Some different doped ternary alloys can be studied by changing
the compound and also the concentration of doping.
c) The PbS crystals of some different morphologies like star,
fishbone, and cross shaped can be synthesized and characterized.
d) The role of other factors like pressure, concentration of
surfactant etc. on the evolution of morphology and size of PbS
micro/nanocrystals can be studied.
e) The hydrothermal and microwave approaches can also be
extended to synthesize other important semiconductor material
with desired morphologies.
It is hoped that this work will encourage further researches in the field of
material science and high pressure physics.
Chapter 4

List of Publications
1. Electronic properties of SnTe: A First Principles Study
G. Sharma, P. Bhambhani, N. Munjal, V. Sharma, and B.K. Sharma
J. Nano. Electron.Phys. 3, 341-347 (2011).

2. Study of phase transition and cohesive energy in MgO


N. Munjal, P. Bhambhani, G. Sharma, V. Vyas, and B. K. Sharma
J. Phys.:Conf. Series. 377, 01267 (2012).

3. First-principles study of B1 to B2 phase transition in PbS


P. Bhambhani, N. Munjal, G. Sharma, and B. K. Sharma
J. Phys.:Conf. Series 377, 01268 (2012).

4. Electron momentum density and X-ray structure factors of copper


N. Munjal, P. Bhambhani, V. Vyas, P. A. Alvi, G. Sharma, and
B.K. Sharma,
W. J. Conden. Matter. Phys. 1, 70-76 (2011).

5. First-principles study of structural properties of MgO


N. Munjal, P. Bhambhani, V. Vyas, G. Sharma, and B.K. Sharma
Presented at NSMAT 2011, Banasthali University, 27-29 March, 2011.

6. Ab-initio study of phase transition and momentum density in PbTe


P. Bhambhani, and G. Sharma
Phase Transitions 86, 551-560 (2013).

7. First-principles study of phase transition in PbSe


P. Bhambhani, and G. Sharma
Presented at 15th Annual Conference of SSCA 2013, Banasthali
University, 24-26 February, 2013.
Chapter 4

8. Ab-initio determination of pressure dependent electronic and optical


properties of lead sulfide for energy applications
P. Bhambhani, and G. Sharma
Advanced Materials Series, Chapter 8, p.p. 327-344, 2013, WILEY-
Scrivener Publishing, USA.

9. Effect of Se doping on structural properties of PbS1-xSex


P. Bhambhani, and G. Sharma
Presented at ENERGY MEET-2013, University of Kota, 02 December,
2013.

10. Investigation of variation in energy-gap of PbS1-xSex with doping


concentration
G. Sharma, and P. Bhambhani
Presented at ENERGY MEET-2013, University of Kota, 02 December,
2013.

11. Synthesis and characterization of PbS micro- and nano-crystals


P. Bhambhani, G. Sharma, V. Sharma, and D. Kumar
Communicated to J. Alloy Compd., 2013.

12. High pressure study of structural and electronic properties of lead


selenide
P. Bhambhani, and G. Sharma
Communicated to Phase Transitions, 2013.