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Table of Contents
Intro; Supervisor's Foreword; Abstract; Publications and Presentations; Work Done in Conjunction with Others; Acknowledgements; Contents; Abbreviations; Symbols; 1 Introduction; 1.1 Energy; 1.1.1 The Problem; 1.1.2 The Solutions; 1.1.3 The Case for Solar Energy; 1.2 Solar Photovoltaics; 1.2.1 Semiconductor Theory; 1.2.2 Photovoltaic Devices; 1.3 A Brief History of Solar Cells; 1.3.1 0th Generation: The Early Years; 1.3.2 1st Generation: Wafer-Based PV; 1.3.3 2nd Generation: Commercial Thin-Film; 1.3.4 3rd Generation: Everything Else, Dependent upon Research Interests.
1.4 Earth-Abundant Thin-Film Solar Cells1.4.1 Why Sulphides?; 1.4.2 Cu-Based Earth-Abundant Post-transition Metal Sulphides; 1.5 Efficiency: The Quintessential Goal of Solar Cell Research?; 1.5.1 Standards; 1.5.2 Record Efficiencies; 1.5.3 A Few Words on Deployment; 1.6 Characterisation of Solar Cells; 1.6.1 Usual Techniques; 1.6.2 The Importance of Electronic Characterisation; 1.7 Overview of the Thesis; 1.7.1 Structure; 1.7.2 Aims; References; 2 Experimental Methods; 2.1 Material Growth Methods; 2.1.1 Single Crystal Growth Methods; 2.1.2 Thin-Film Growth Methods; 2.2 Ultrahigh Vacuum.
2.2.1 The Necessity for Vacuum2.2.2 Achieving UHV; 2.2.3 A 3-Chamber Surface Science System; 2.2.4 A Single-Chamber Electronic Characterisation System; 2.3 Photoemission Spectroscopy; 2.3.1 Principles and Theory; 2.3.2 Operation and Implementation; 2.3.3 Spectrometer Calibrations; 2.3.4 Spectral Analysis; 2.4 Density Functional Theory; 2.4.1 Introduction; 2.4.2 Implementation; 2.5 Fourier Transform Infrared Spectroscopy; 2.5.1 Principles and Theory; 2.5.2 Operation and Implementation; 2.6 X-Ray Diffraction; 2.6.1 Principles and Theory; 2.6.2 Operation and Implementation.
2.7 Raman Spectroscopy2.7.1 Principles and Theory; 2.7.2 Operation and Implementation; 2.8 Energy-Dispersive X-Ray Spectroscopy; 2.9 Summary; References; 3 The Electronic Structure of CuSbS2 for Use as a PV Absorber; 3.1 CuSbS2: The Material; 3.1.1 History; 3.1.2 CuSbS2 as a Solar Absorber; 3.1.3 Structure; 3.1.4 Motivation and Scope of This Study; 3.2 Experimental Details; 3.2.1 Growth of CuSbS2 Films; 3.2.2 Characterisation of CuSbS2 Films; 3.3 Electronic Structure Studies of High-Quality CuSbS2 Films; 3.3.1 Phase-Purity; 3.3.2 XPS Core-Level Analysis; 3.3.3 Natural Band Alignments.
3.3.4 Density of States Analysis3.4 Further Effects of Contamination and the Thermal Treatment of CuSbS2; 3.4.1 The Effects of Contamination; 3.4.2 The Effects of the Thermal Treatment; 3.5 Summary; References; 4 The Electronic Structure of Cu3BiS3 for Use as a PV Absorber; 4.1 Cu3BiS3: The Material; 4.1.1 History and Uses; 4.1.2 Cu3BiS3 as a Solar Absorber; 4.1.3 Structure; 4.1.4 Motivation and Scope of This Study; 4.2 Experimental Details; 4.2.1 Growth of Cu3BiS3 Films; 4.2.2 Characterisation of Cu3BiS3; 4.3 Electronic Structure Studies of Cu3BiS3; 4.3.1 Phase-Purity.
1.4 Earth-Abundant Thin-Film Solar Cells1.4.1 Why Sulphides?; 1.4.2 Cu-Based Earth-Abundant Post-transition Metal Sulphides; 1.5 Efficiency: The Quintessential Goal of Solar Cell Research?; 1.5.1 Standards; 1.5.2 Record Efficiencies; 1.5.3 A Few Words on Deployment; 1.6 Characterisation of Solar Cells; 1.6.1 Usual Techniques; 1.6.2 The Importance of Electronic Characterisation; 1.7 Overview of the Thesis; 1.7.1 Structure; 1.7.2 Aims; References; 2 Experimental Methods; 2.1 Material Growth Methods; 2.1.1 Single Crystal Growth Methods; 2.1.2 Thin-Film Growth Methods; 2.2 Ultrahigh Vacuum.
2.2.1 The Necessity for Vacuum2.2.2 Achieving UHV; 2.2.3 A 3-Chamber Surface Science System; 2.2.4 A Single-Chamber Electronic Characterisation System; 2.3 Photoemission Spectroscopy; 2.3.1 Principles and Theory; 2.3.2 Operation and Implementation; 2.3.3 Spectrometer Calibrations; 2.3.4 Spectral Analysis; 2.4 Density Functional Theory; 2.4.1 Introduction; 2.4.2 Implementation; 2.5 Fourier Transform Infrared Spectroscopy; 2.5.1 Principles and Theory; 2.5.2 Operation and Implementation; 2.6 X-Ray Diffraction; 2.6.1 Principles and Theory; 2.6.2 Operation and Implementation.
2.7 Raman Spectroscopy2.7.1 Principles and Theory; 2.7.2 Operation and Implementation; 2.8 Energy-Dispersive X-Ray Spectroscopy; 2.9 Summary; References; 3 The Electronic Structure of CuSbS2 for Use as a PV Absorber; 3.1 CuSbS2: The Material; 3.1.1 History; 3.1.2 CuSbS2 as a Solar Absorber; 3.1.3 Structure; 3.1.4 Motivation and Scope of This Study; 3.2 Experimental Details; 3.2.1 Growth of CuSbS2 Films; 3.2.2 Characterisation of CuSbS2 Films; 3.3 Electronic Structure Studies of High-Quality CuSbS2 Films; 3.3.1 Phase-Purity; 3.3.2 XPS Core-Level Analysis; 3.3.3 Natural Band Alignments.
3.3.4 Density of States Analysis3.4 Further Effects of Contamination and the Thermal Treatment of CuSbS2; 3.4.1 The Effects of Contamination; 3.4.2 The Effects of the Thermal Treatment; 3.5 Summary; References; 4 The Electronic Structure of Cu3BiS3 for Use as a PV Absorber; 4.1 Cu3BiS3: The Material; 4.1.1 History and Uses; 4.1.2 Cu3BiS3 as a Solar Absorber; 4.1.3 Structure; 4.1.4 Motivation and Scope of This Study; 4.2 Experimental Details; 4.2.1 Growth of Cu3BiS3 Films; 4.2.2 Characterisation of Cu3BiS3; 4.3 Electronic Structure Studies of Cu3BiS3; 4.3.1 Phase-Purity.