Perovskite Photovoltaics and Optoelectronics: From Fundamentals to Advanced Applications

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Perovskite Photovoltaics and Optoelectronics Discover a one-of-a-kind treatment of perovskite photovoltaics In less than a decade, the photovoltaics of organic-inorganic halide perovskite materials has surpassed the efficiency of semiconductor compounds like CdTe and CIGS in solar cells. In Perovskite Photovoltaics and Optoelectronics: From Fundamentals to Advanced Applications, distinguished engineer Dr. Tsutomu Miyasaka delivers a comprehensive exploration of foundational and advanced topics regarding halide perovskites. It summarizes the latest information and discussion in the field, from fundamental theory and materials to critical device applications. With contributions by top scientists working in the perovskite community, the accomplished editor has compiled a resource of central importance for researchers working on perovskite related materials and devices. This edited volume includes coverage of new materials and their commercial and market potential in areas like perovskite solar cells, perovskite light-emitting diodes (LEDs), and perovskite-based photodetectors. It also includes: A thorough introduction to halide perovskite materials, their synthesis, and dimension control Comprehensive explorations of the photovoltaics of halide perovskites and their historical background Practical discussions of solid-state photophysics and carrier transfer mechanisms in halide perovskite semiconductors In-depth examinations of multi-cation anion-based high efficiency perovskite solar cells Perfect for materials scientists, crystallization physicists, surface chemists, and solid-state physicists, Perovskite Photovoltaics and Optoelectronics: From Fundamentals to Advanced Applications is also an indispensable resource for solid state chemists and device/electronics engineers. Cover Title Page Copyright Contents Preface Chapter 1 Research Background and Recent Progress of Perovskite Photovoltaics 1.1 Introduction 1.2 History of Halide Perovskite Photovoltaics 1.2.1 Discovery of the Perovskite Crystal Form 1.2.2 Discovery of Metal Halide Perovskites 1.2.3 Beginning of Halide Perovskite Photovoltaics 1.3 Semiconductor Properties of Organo‐Lead Halide Perovskites 1.4 Working Principle of Perovskite Photovoltaics 1.5 Compositional Engineering for the Halide Perovskite Absorbers 1.6 Strategies to Stabilize Halide Perovskite Solar Cells 1.6.1 Bridging the Gap Between Efficiency and Stability 1.6.2 Enhancing Intrinsic Stability of Halide Perovskites 1.6.3 External and Environmental Stability 1.7 Progress of All inorganic and Lead‐Free Perovskites 1.8 Enhancing Efficiency of Low‐Cost Tandem Solar Cells 1.9 Space Applications of the Perovskite Solar Cells 1.10 Conclusion and Perspectives References Chapter 2 Halide Perovskite Materials, Structural Dimensionality, and Synthesis 2.1 Three‐Dimensional and Low‐Dimensional Semiconductors: Organic‐Inorganic Perovskites 2.2 Perovskite‐Type Metal Halide Compounds 2.3 Preparation of Two‐ to Three‐Dimensional Lead Halide‐Based Perovskite Compounds 2.3.1 Spin‐Coating Method for Synthesis 2.3.2 Vacuum Evaporation Method 2.3.3 Two‐Step Deposition Method 2.3.4 Self‐Intercalation Method 2.3.5 Layer‐by‐Layer Self‐Assembly Method 2.3.6 Langmuir–Blodgett Method 2.4 Conclusion References Chapter 3 Microstructures and Grain Boundaries of Halide Perovskite Thin Films 3.1 Introduction 3.2 Microstructure Characteristics 3.2.1 The Nature of Grain Boundaries (GBs) 3.2.2 Grain Size and Distribution 3.2.3 Crystallographic Texture 3.3 Microstructural Evolution in HP Thin Films 3.3.1 Genesis of Microstructure 3.3.2 Grain Growth 3.4 Influence of Microstructures and GBs on Performance and Stability 3.4.1 Grain Size Effects 3.4.2 Effects of the Nature of GBs 3.4.3 Crystallographic Texture Effects 3.5 Outlook Acknowledgments References Chapter 4 Defect Properties of Halide Perovskites for Photovoltaic Applications 4.1 Introduction 4.2 Defect Properties of ABX3 Halide Perovskites 4.2.1 Pb‐Based Halide Perovskites 4.2.1.1 Point Defects 4.2.1.2 Ideal Grain Boundaries 4.2.1.3 Ideal Surfaces 4.2.1.4 Surfaces and Boundaries in Real Thin Films 4.2.2 Sn‐Based Halide Perovskites 4.2.3 Ge‐Based Halide Perovskites 4.3 Defect Properties of Halide Perovskites Beyond ABX3 4.3.1 A2BX6 Halide Perovskite Derivatives 4.3.2 A3B2X9 Layered Halide Perovskites 4.3.3 A2B(I)B(III)X6 Halide Double Perovskites 4.4 Conclusion References Chapter 5 Physics of Perovskite Solar Cells: Efficiency, Open‐Circuit Voltage, and Recombination 5.1 Theory 5.1.1 Power‐Conversion Efficiency of a Solar Cell 5.1.2 The Ideal Solar Cell: Shockley–Queisser Limit 5.1.3 Radiative Limit, Reciprocity, and Detailed Balance 5.1.4 Non‐radiative Recombination and Role of Contacts 5.2 Determining Efficiency and Characterizing Recombination 5.2.1 The Current Density–Voltage (J–V) Curve 5.2.2 Determination of the Bandgap and the “Voltage Deficit” 5.2.3 Electroluminescence 5.2.4 Photoluminescence 5.2.5 Transient Photoluminescence 5.2.6 Electrochemical Impedance Spectroscopy 5.2.7 Transient Photovoltage Decay and IMVS 5.2.8 The Ideality Factor 5.2.9 Space Charge‐Limited Currents 5.3 Recombination in Perovskite Solar Cells: What We Know 5.3.1 Intrinsic Properties of the Perovskite Crystal 5.3.1.1 Relatively High Absorption and Fast Radiative Recombination 5.3.1.2 Shallow Defects and Defect Tolerance 5.3.1.3 High Dielectric Constant 5.3.1.4 Low‐Frequency Lattice Phonons 5.3.1.5 Further Explanations for Reduced Recombination 5.3.2 Impurities 5.3.3 Grain Boundaries 5.3.4 Interfaces: Between Alignment and Passivation 5.3.5 Mobile Ions 5.4 Summary and Outlook Acknowledgments References Chapter 6 Ionic/Electronic Conduction and Capacitance of Halide Perovskite Materials 6.1 Introduction 6.2 Overview 6.3 Carrier Transport 6.3.1 General Determination of Transport Coefficients, Diffusion Coefficient, and Mobility 6.3.2 Mixed Ionic/Electronic Conduction and Time Constants 6.3.3 Measurement of Ionic Conductivity by Galvanostatic Transient Method 6.3.4 Measurement of Ionic Diffusion by Impedance Spectroscopy 6.3.5 Ionic Drift Causes Suppression of Luminescence 6.4 Interpretation of Capacitances in Semiconductor Devices 6.4.1 Dielectric Relaxation 6.4.2 Chemical Capacitance 6.4.3 Electrode Polarization 6.4.4 Depletion Capacitance at the Schottky Barrier 6.4.5 Capacitance Associated to Defect Levels 6.5 Surface Polarization and Capacitances of MHP 6.5.1 General Properties of the Capacitance of MHP 6.5.2 Complexity of Mott–Schottky Analysis 6.5.3 Measurement of Trap Density 6.6 Impedance Spectroscopy and the Equivalent Circuit Model 6.6.1 Interpretation of Equivalent Circuits 6.6.2 Negative Capacitance Phenomena 6.6.3 Application of IS Model to Understanding of Memory Effects 6.7 Intensity‐Modulated Photocurrent Spectroscopy 6.8 Dynamic Response in Time Transient Methods 6.8.1 Time Transients of Photovoltage and Charge–Discharge Methods 6.8.2 Charge–Discharge Methods 6.8.3 Significance of Surface Charging in MHP 6.9 Conclusions References Chapter 7 Hysteresis of I–V Performance: Its Origin and Engineering for Elimination 7.1 Introduction 7.2 Hysteresis in Current–Voltage Performance 7.3 Material and Structure Design to Reduce Hysteresis 7.3.1 Grain Boundary Engineering 7.3.2 Interfacial Engineering 7.3.3 Defect Engineering 7.4 Effect of Alkali Cation Doping 7.4.1 Reduction in Hysteresis by KI Doping: A Universal Approach 7.4.2 Passivation Effect of Excess KI 7.4.3 Location of Potassium Ion in Perovskite 7.4.4 In situ Photoluminescence (PL) as a Tool to Measure Ion Migration Kinetics 7.5 Summary References Chapter 8 High‐Efficiency Solar Cells with Polyelemental, Multicomponent Perovskite Materials 8.1 Introduction 8.2 Polyelemental, Multicomponent Engineering 8.2.1 Single‐Cation Perovskites 8.2.2 Double‐Cation Perovskites: Stabilizing the Black Phase 8.2.3 Triple‐Cation Perovskites: Stable and Reproducible Devices 8.2.4 Quadruple‐Cation Perovskite: Improvement of Long‐Term Device Stability 8.2.5 Methylammonium‐Free Perovskite: Staying in the Black Phase with Fewer Components 8.3 Conclusions References Chapter 9 All‐Inorganic Perovskite Photovoltaics 9.1 Introduction 9.2 All‐Inorganic Lead Halide Perovskites 9.2.1 Cesium Lead Iodide (CsPbI3): Black‐Phase Stabilization 9.2.1.1 Additive Approach 9.2.1.2 Quantum Dot‐Induced Black‐Phase Stabilization 9.2.1.3 Stabilization by Surface Treatment 9.2.1.4 B‐Site Doping 9.2.2 Cesium Lead Bromide (CsPbBr3) 9.2.3 Cesium Lead Mixed‐Halide Perovskites (CsPbI3−xBrx) 9.3 All‐Inorganic Tin Halide Perovskites 9.3.1 CsSnX3 (X = I, Br, Cl) 9.3.2 Cs2SnX6 (X = I, Br) 9.4 All‐Inorganic Silver‐Bismuth Halides 9.4.1 Cs2M1(I)M2(III)X6 Double Perovskite 9.4.2 AgaBibXa+3b Rudorffites 9.5 Summary and Outlook Acknowledgments References Chapter 10 Sn‐Based Halide Perovskite Solar Cells 10.1 Introduction 10.2 Sn–Pb Perovskite Solar Cells 10.2.1 Background 10.2.2 Stabilization of Sn(II) Ions 10.2.3 Efficiency Enhancement 10.2.4 Interfacial Engineering and Device Architecture 10.3 Pb‐free Sn Perovskite Solar Cells 10.3.1 Background 10.3.2 Ge‐Doped Sn Perovskites 10.3.3 Efficiency Enhancement by Grain Boundary Passivation 10.4 Conclusion References Chapter 11 Quantum Dots of Halide Perovskite 11.1 Introduction 11.2 The Synthesis of Halide Perovskite QDs 11.2.1 Ligand‐Assisted Reprecipitation Method 11.2.2 Hot Injection Method 11.2.3 Ion Exchange Reactions 11.3 The Photophysics of Halide Perovskite QDs 11.3.1 Tunable Bandgap 11.3.2 Multiple Exciton Generation 11.3.3 Hot Electron Extraction 11.4 Surface Passivation of Halide Perovskite QDs 11.4.1 Surface Ligand Engineering 11.4.2 Post‐Synthetic Treatment 11.4.3 Surface Coating 11.5 Applications of Halide Perovskite QDs 11.5.1 Light‐Emitting Diode (LED) 11.5.2 Solar Cells 11.6 Conclusion and Outlook References Chapter 12 Perovskite Light‐Emitting Diode Technologies 12.1 Introduction 12.2 Physics Behind Operation of Perovskite‐Based LEDs 12.2.1 Photon Generation by Electrostimulation 12.2.2 Charge Balance in PeLEDs 12.2.3 Non‐radiative Losses in PeLEDs 12.2.4 Photon Recycling in PeLEDs 12.3 Progress on Perovskite‐Based LEDs 12.3.1 Literature Review 12.3.1.1 Near‐Infrared PeLEDs 12.3.1.2 Red PeLEDs 12.3.1.3 Green PeLEDs 12.3.1.4 Blue PeLEDs 12.4 Challenges and Outlook 12.5 Conclusions Acknowledgments References Chapter 13 Perovskites Enabled Highly Sensitive and Fast Photodetectors 13.1 Introduction 13.2 Why Perovskites for Photodetectors 13.3 Types of Perovskite Photodetectors 13.3.1 Photodiodes 13.3.1.1 Broadband Photodiodes 13.3.1.2 Narrowband Photodiodes 13.3.2 Photoconductors 13.3.2.1 Vertical Photoconductors 13.3.2.2 Lateral Photoconductors 13.3.3 Phototransistor 13.4 Conclusion Acknowledgment Disclaimer References Chapter 14 Metal Halide Perovskites for Sensitive X‐ray Detectors 14.1 Introduction 14.2 Working Mechanism of X‐ray Detectors 14.3 Material Properties of Ideal X‐ray Detectors 14.4 Conventional X‐ray Detectors 14.5 Perovskite X‐ray Detectors 14.5.1 Direct Perovskite X‐ray Detectors 14.5.2 Perovskite X‐ray Scintillators 14.6 Characterization of X‐ray Flat Panels 14.6.1 Sensitivity 14.6.2 DQE 14.6.3 MTF 14.6.4 Pixel‐to‐Pixel Uniformity 14.6.5 Imaging Lag 14.6.6 Ghosting 14.7 Summary and Outlook Acknowledgement References Chapter 15 Perovskite‐Based Multijunction Solar Cells 15.1 Introduction 15.2 Why Perovskites? 15.3 How to Make an Efficient Perovskite‐Based Tandem? 15.3.1 Low Bandgap Solar Cell 15.3.1.1 Silicon 15.3.1.2 Chalcopyrites: CIGS and CIS 15.3.1.3 Sn/Pb Low Bandgap Perovskites 15.3.2 Recombination Junction 15.3.2.1 Nanocrystalline Silicon Junction 15.3.2.2 Recombination Layer for All‐Perovskite Tandems 15.3.3 Wide‐Bandgap Perovskite Solar Cell 15.3.4 Mitigating Optical Losses 15.3.4.1 Parasitic Absorption Losses 15.3.4.2 Reflection Losses: Front, Middle, and Back 15.3.4.3 Textured Substrates 15.3.4.4 Current Matching Versus Power Matching 15.4 Toward Commercialization 15.4.1 Energy Yield 15.4.2 Cost 15.4.3 Market Choice 15.5 Beyond Tandems: Triple? 15.6 Concluding Remarks References Index EULA