Growth And Characterization Of Ternary Chalcogenide Thin Films For Efficient Solar Cells And Possible Industrial Applications

Project and Seminar Material for Physics

Abstract

Ternary thin films of Iron Copper Sulphide (FeCuS), Iron Zinc Sulphide (FeZnS), Lead Silver Sulphide (PbAgS), Copper Silver Sulphide (CuAgS) and Copper Zinc Sulphide (CuZnS) were grown using cheap and simple solution growth technique with EDTA, TEA and NH3 as complexing agents. The deposited films were characterized using PYE-UNICO-UV-2102 PC spectrophotometer, and optical microscopy. The results suggest that some of the films have crystal structures. From the spectral analysis of absorbance/transmittance, the optical and solid state properties were deduced. The other optical properties so obtained include the reflectance, absorption coefficient, refractive index, extinction coefficient, optical conductivity and thickness, while the solid state properties are dielectric constant and band gap energy.

For all the five categories of thin films grown (i.e. FeCuS, FeZnS, PbAgS, CuAgS and CuZnS), absorbance was high in UV and low in VIS-NIR-regions, while the transmittance were low in UV-region and high in VIS-NIR-regions. The reflectances were high in UV-region and low in the VIS-NIR-regions. For FeCuS, FeZnS, PbAgS, CuAgS and CuZnS, the absorption coefficient ranged from 0.1×106 m-1 to 1.65×106 m-1, 0.2×106 m-1 to 2.3×106 m-1, 0.5×106 m-1 to 0.9×106 m-1, 0.5×106 m-1 to 1.28×106 m-1 and 0.24×106 m-1 to 1.6×106 m-1, respectively. The real part of the refractive index ranged from 1.2 to 2.3, 0.72 to 2.3, 0.1 to 2.3, 1.94 to 2.28 and 1.6 to 2.3, respectively.

The corresponding values of optical conductivity ranged from 0.03×1014 s-1 to 0.6×1014 s-1, 0.07×1014 s-1, 0.06×1014 s-1 to 0.6×1014 s-1, 0.24×1014 s-1 to 0.6×1014 s-1 and 0.12×1014 s-1 to 0.6×1014 s-1, respectively. The extinction coefficient, ranged from 0.005 to 0.038, 0.004 to 0.056, 0.010 to 0.140, 0.025 to 0.064 and 0.008 to 0.082, respectively. The direct band gap ranged from 2.4eV to2.8eV for FeCuS, 2.9eV for FeZnS, 1.5eV to 2.1eV for PbAgS, 2.3eV for CuAgS and 2.2eV to 2.4eV for CuZnS. The values of the indirect band gap were in the range 0.6eV to 1.0eV for FeCuS, 1.9eV for FeZnS, 0.3eV to 0.8eV for PbAgS, 1.1eV for CuAgS and 0.4eV to 0.9eV for CuZnS.

The real part of the dielectric constant ranged from 1.4 to 5.2, 0.7 to 5.2, 0.4 to 5.2, 3.8 to 5.2 and 2.2 to 5.2, respectively, while the corresponding imaginary part of the dielectric constant ranged from 0.008 to 0.136, 0.008 to 0.164, 0.010 to 0.390, 0.100 to 0.290 and 0.030 to 0.360, respectively. The range of band gaps, 1.5eV to 2.9eV makes the films suitable for solar cells fabrication; this is in agreement with the finding for the film FeCdS.

Title ii
Certification iii
Dedication iv
Acknowledgement .v
Table of Contents vi-xiii
List of Figures xiv-xvi
List of Plates xvii
List of Slides xviii
List of Set Ups xvii
Abstract xviii-xix

Chapter One

1.1.0 Introduction 1
1.2.0 Benefits of Thin Films 2
1.3.0 Aim and Objectives of the Study 3-4

Chapter Two

2.1.0 Optical and Solid State Properties of Thin Film -5
2.1.1 Transmittance 5-6
2.1.2 Absorbance 6
2.1.3 Reflectance 7
2.1.4 Absorption Coefficient 7-8
2.1.5 Optical Density 8-9
2.2.0 Band gap and Absorption Edge 9-12
2.2.1 Absorption Edge 12-13
2.2.2 Optical Constants 13-14
2.2.3 Dielectric Constant 14-15
2.2.4 Optical Conductivity 15
2.2.5 Extinction Coefficient Factor 15
2.3.0 Dispersion 15-16
2.4.0 Photoconductivity 16-17
2.5.0 Luminescence 17-18
2.6.0 Electrical Conductivity 18
2.7.0 Thermal Conductivity 18-19
2.8.0 Spectral Selective Surfaces Aspect of Solar Energy Application 19
2.8.1 Spectral Selectivity 19-20
2.8.2 Solar Spectral Selective Absorber Surfaces 20-21
2.8.3 Semiconductor-Metal tandems 21
2.8.4 Heat Mirrors 21-22
2.8.5 Dark Mirrors 22
2.8.6 Antireflection Coatings 22-23
2.8.7 Spectral Splitting and Cold Mirror Coatings 23
2.8.8 Radiative Cooling Materials 23
2.8.9 Window Coatings 23-24
2.9.0 Solar Control Coatings 24
2.9.1 Low Thermal Transmittance 24
2.9.2 Materials for Solar Control and Low Thermal Transmittance 24-25
2.9.3 Window Coatings with Dynamic Properties 25-26

Chapter Three

3.0 Methods for Thin Film Growth 27
3.1.1 Thermal Evaporation 27-29
3.1.2 Epitaxial Growth 29-30
3.1.2.1 Molecular Beam Epitaxial (MBE) 30-32
3.1.2.2 Liquid Phase Epitaxy 32
3.1.3 Sputtering 32-34
3.1.4 Chemical Vapour Deposition (CVD) 34-36
3.1.5 Spray Pyrolysis 37
3.1.6 Plasma Technique 37-38
3.1.7 Sol-gel Thin Film Formation 38
3.1.8 Precursor Sol 38-39
3.1.8.1 Sol-gel Dip Coating 39
3.1.8.2 Spin Coating 39-40
3.1.8.3 Spin Deposition of Halide and Chalcogenide Films 40-41
3.1.9 The Solution Growth Technique 41-44
3.1.9.1 Thin Film Condensation Formation Mechanism 44-45
3.1.9.2 Doping by Chemical Bath Deposition 45

Chapter Four

The Measurement Techniques of Thin Film Characteristics and Materials 46
4.1.0 Measurement Techniques of Thin Film Characteristics 46
4.1.1 Film Thickness 46
4.1.1.1 Micro balance (gravimetric ) Technique 47
4.1.1.2 Optical Technique 47-48
4.1.2 Absorbance/Transmittance Measurement 48
4.1.3 Method of Determining the Composition of Thin Films 48-49
4.1.3.1 Atomic Absorption Spectroscopic (AAS) Method 49
4.1.3.2 X-ray Fluorescence 49-50
4.1.3.3 Infrared Spectroscopy 50-51
4.1.3.4 Qualitative and Quantitative Chemical Analysis (QCA) 52
4.2.0 Structural Characterization 52-53
4.2.1 Crystallographic Structure and Topography 53-54
4.2.1 Transmission Electron Microscopy (TEM) 53-54
4.2.2 Surface Structure 54
4.2.2.1 LEED Technique 54
4.2.2.2 RHEED Technique 54-55
4.2.2.3 Photo Electron Spectroscopy (PES) 55
4.2.2.4 Optical Microscopy 55-56
4.3.0 Methodology 57-58
4.3.1 Iron Copper Sulphide 58-60
4.3.2 Optical and Solid State Characterization 60
4.3.3 Film Thickness Measurement 60-61
4.4. Morphological Analysis 61

Chapter Five

5.0 Results and Observations 62
5.1 Optical Properties of Iron Copper Sulphide (FeCuS) 62
5.1.1 Absorbance (A) 62
5.1.2 Transmittance (T) 62
5.1.3 Reflectance (R ) 62-63
5.1.4 Absorption Coefficient ( Î± ) 63
5.1.5 Refractive Index (n) 63
5.1.6 Optical Conductivity (Ïƒo ) 64
5.1.7 Extinction Coefficient ( k) 64
5.2 Solid State Properties 64
5.2.1 Band gap Energy (Eg) 64-65
5.2.2 Dielectric Constant (real part) (Îµ r ) 65
5.2.3 Dielectric Constant ( imaginary part ) (Îµ i ) 65
5.3 Optical Properties of Iron Zinc Sulphide (FeZnS) 65
5.3.1 Absorbance (A) 65
5.3.2 Transmittance (T) 66
5.3.3 Reflectance (R) .66
5.3.4 Absorption Coefficient (Î± ) 66
5.3.5 Refractive Index (n) 66-67
5.3.6 Optical Conductivity (Ïƒo) 67
5.3.7 Extinction Coefficient ( k) 67
5.4 Solid State Properties 67
5.4.1 Band gap Energy (Eg) 67
5.4.2 Dielectric Constant (real ) (Îµ r) 68
5.4.3 Dielectric Constant (imaginary part ) (Îµ i ) 68
5.5 Optical Properties of Lead Silver Sulphide ( PbAgS) 68
5.5.1 Absorbance (A) 68
5.5.2 Transmittance ( T ) 69
5.5.3 Reflectance ( R ) 69
5.5.4 Absorption Coefficient (Î± ) 69
5.5.5 Refractive Index ( n) 69-70
5.5.6 Optical Conductivity (Ïƒo ) 70
5.5.7 Extinction Coefficient ( k ) 70
5.6 Solid State Properties 71
5.6.1 Band gap Energy ( Eg ) 71
5.6.2 Dielectric Constant (real part ) (Îµ r ) 71
5.6.3 Dielectric Constant ( imaginary part ) (Îµ i ) 71-72
5.7 Optical Properties of Copper Silver Sulphide (CuAgS) 72
5.7.1 Absorbance (A) 72
5.7.2 Transmittance ( T ) 72
5.7.3 Reflectance ( R ) 72
5.7.4 Absorption Coefficient (Î± ) 73
5.7.5 Refractive Index (n ) 73
5.7.6 Optical Conductivity (Ïƒo ) 73
5.7.7 Extinction Coefficient ( k) 73
5.8 Solid State Properties 73
5.8.1 Band gap Enegry ( Eg ) 73-74
5.8.2 Dielectric Constant (real part ) (Îµ r) 74
5.8.3 Dielectric Constant (imaginary part ) (Îµ i ) 74
5.9 Optical Properties of Copper Zinc Sulphide (CuZnS) 74
5.9.1 Absorbance ( A ) 74
5.9.2 Transmittance ( T ) 75
5.9.3 Reflectance ( R ) 75
5.9.4 Absorption Coefficient (Î± ) 75-76
5.9.5 Refractive Index ( n) 76
5.9.6 Optical Conductivity (Ïƒo) 76
5.9.7 Extinction Coefficient ( k ) 77
5.10 Solid State Properties 77
5.10.1 Band gap Energy (Eg) 77-78
5.10.2 Dielectric Constant (real part ) (Îµ r ) 78
5.10.3 Dielectric Constant ( imaginary part ) (Îµ i ) 78

Chapter Six

6.0 Analysis and Discussion 80
6.1 The Spectral Analysis 80
6.2 Other Optical Properties 80
6.3 Solid State Properties 80-81

Chapter Seven

Conclusion and Recommendations 82
7.0 Conclusion 82-84
7.1 Recommendation 85
References 86-99
Appendix A. Figures 100-154
Appendix B Plates 155-157
Appendix C Slides 158-159
Appendix D Set Ups 160-161

List Of Figures

Figure 5.1 Graph of absorbance (A) versus wavelength for FeCuS thin film 100
Figure 5.2 Graph of transmittance (T) versus wavelength for FeCuS thin film 101
Figure 5.3 Graph of reflectance (R) versus wavelength for FeCuS thin film 102
Figure 5.4 Graph of absorption coefficient versus photon energy for FeCuS thin film 103
Figure 5.5 Graph of refractive index versus photon energy for FeCuS thin film 104
Figure 5.6 Graph of optical conductivity versus photon energy for FeCuS thin film 105
Figure 5.7 Graph of extinction coefficient versus photon energy for FeCuS thin film 106
Figure 5.8 Graph of Î±2 versus photon energy for FeCuS thin film 107
Figure 5.9 Graph of Î±1/2 versus photon energy for FeCuS thin film 108
Figure 5.10 Graph of dielectric constant (real part) versus photon energy for FeCuS thin film.109
Figure 5.11 Graph of dielectric constant (imaginary part) versus photon energy for FeCuS thin film 110
Figure 5.12 Graph of absorbance (A) versus wavelength for FeZnS thin film 111
Figure 5.13 Graph of transmittance (T) versus wavelength for FeZnS thin film 112
Figure 5.14 Graph of reflectance (R ) versus wavelength for FeZnS thin film 113
Figure 5.15 Graph of absorption coefficient versus photon energy for FeZnS thin film 114
Figure 5.16 Graph of refractive index versus photon energy for FeZnS thin film 115
Figure 5.17 Graph of optical conductivity versus photon energy for FeZnS thin film 116
Figure 5.18 Graph of extinction coefficient versus photon energy for FeZnS thin film 117
Figure 5.19 Graph of Î±2 versus photon energy for FeZnS thin film 118
Figure 5.20 Graph of Î±1/2 versus photon energy for FeZnS thin film 119
Figure 5.21 Graph of dielectric constant (real part) versus photon energy for FeZnS thin film.120
Figure 5.22 Graph of dielectric constant (imaginary part) versus photon energy for FeZnS thin film 121
Figure 5.23 Graph of absorbance (A) versus wavelength for PbAgS thin film 122
Figure 5.24 Graph of transmittance (T) versus wavelength for PbAgS thin film 123
Figure 5.25 Graph of reflectance (R ) versus wavelength for PbAgS thin film 124
Figure 5.26 Graph of absorption coefficient versus photon energy for PbAgS thin film 125
Figure 5.27 Graph of refractive index versus photon energy for PbAgS thin film 126
Figure 5.28 Graph of optical conductivity versus photon energy for PbAgS thin film 127
Figure 5.29 Graph of extinction coefficient versus photon energy for PbAgS thin film 128
Figure 5.30 Graph of Î±2 versus photon energy for PbAgS thin film 129
Figure 5.31 Graph of Î±1/2 versus photon energy for PbAgS thin film 130
Figure 5.32 Graph of dielectric constant (real part) versus photon energy for PbAgS thin film.131
Figure 5.33 Graph of dielectric constant (imaginary part) versus photon energy for PbAgS thin film 132
Figure 5.34 Graph of absorbance (A) versus wavelength for CuAgS thin film 133
Figure 5.35 Graph of transmittance (T) versus wavelength for CuAgS thin film 134
Figure 5.36 Graph of reflectance (R ) versus wavelength for CuAgS thin film 135
Figure 5.37 Graph of absorption coefficient versus photon energy for CuAgS thin film 136
Figure 5.38 Graph of refractive index versus photon energy for CuAgS thin film 137
Figure 5.39 Graph of optical conductivity versus photon energy for CuAgS thin film 138
Figure 5.40 Graph of extinction coefficient versus photon energy for CuAgS thin film 139
Figure 5.41 Graph of Î±2 versus photon energy for CuAgS thin film 140
Figure 5.42 Graph of Î±1/2 versus photon energy for CuAgS thin film 141
Figure 5.43 Graph of dielectric constant (real part) versus photon energy for CuAgS thin film 142
Figure 5.44 Graph of dielectric constant (imaginary part) versus photon energy for CuAgS thin film 143
Figure 5.45 Graph of absorbance (A) versus wavelength for CuZnS thin film 144
Figure 5.46 Graph of transmittance versus wavelength for CuZnS thin film 145
Figure 5.47 Graph of reflectance (R ) versus wavelength for CuZnS thin film 146
Figure 5.48 Graph of absorption coefficient versus photon energy for CuZnS thin film 147
Figure 5.49 Graph of refractive index versus photon energy for CuZnS thin film 148
Figure 5.50 Graph of optical conductivity versus photon energy for CuZnS thin film 149
Figure 5.51 Graph of extinction coefficient versus photon energy for CuZnS thin film 150
Figure 5.52 Graph of Î±2 versus photon energy for CuZnS thin film 151
Figure 5.53 Graph of Î±1/2 versus photon energy for CuZnS thin film 152
Figure 5.54 Graph of dielectric constant (real part) versus photon energy for CuZnS thin film.153
Figure 5.55 Graph of dielectric constant (imaginary part) versus photon energy for CuZnS thin film 154

List Of Plates

Plate 5.1 Photomicrograph of FeCuS 155
Plate 5.2 Photomicrograph of FeZnS 156
Plate 5.3 Photomicrograph of PbAgS 156
Plate 5.4 Photomicrograph of CuAgS 157
Plate 5.5 Photomicrograph of CuZnS 157

List Of Slides

Slide 5.1 Picture of FeCuS thin film 158
Slide 5.2 Picture of FeZnS thin film 158
Slide 5.3 Picture of PbAgS thin film 159
Slide 5.4 Picture of CuAgS thin film 159
Slide 5.5 Picture of CuZnS thin film 159

List Of Set Ups

Set Up 3.1 Experimental Set Up 160
Set up 4.1 Flow Chart for the Growth Process 161

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