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Halide Perovskite Semiconductors: Structures, Characterization, Properties, and Phenomena
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Contents
Preface
1. Introduction to Perovskite
1.1 Evolution of Perovskite
1.2 Structure of Perovskite
1.3 Property and Application of Perovskite
1.4 Summary and Outlook
References
2. Halide Perovskite Single Crystals
2.1 Introduction
2.2 Crystal Structure
2.2.1 Lead‐Based Perovskite Single Crystals
2.2.2 Lead‐Free Perovskite Single Crystals
2.2.3 All‐Inorganic Perovskite Single Crystals
2.3 Synthesis Methods
2.3.1 Antisolvent Vapor‐Assisted Crystallization (AVC) Method
2.3.2 Solution Temperature Lowering (STL) Method
2.3.3 Bridgman Method
2.3.4 Slow Evaporation Method
2.3.5 Inverse Temperature Crystallization (ITC) Method
2.3.6 Methods for 2D and 1D Perovskite Single Crystals
2.4 Optoelectronic Properties of Halide Perovskite Single Crystals
2.4.1 UV–Vis Absorption, Photoluminescence (PL), and Transient Decays: TRPL and TPV
2.4.2 Electronic Properties
2.4.2.1 Space‐Charge‐Limited Current (SCLC)
2.4.2.2 Impedance Spectroscopy (IS)
2.5 Applications
2.5.1 Photodetectors
2.5.2 X‐Ray Detection
2.5.3 γ‐Ray Detection and Scintillators
2.5.4 Solar Cells
2.5.5 Light Emitting Diodes
2.5.6 Memristors
Acknowledgments
References
3. Halide Perovskite Nanocrystals
3.1 Introduction
3.2 Methodology
3.2.1 Hot‐injection (HI) Method
3.2.2 Ligand‐assisted Reprecipitation (LARP) Method
3.2.3 Microwave‐assisted Synthesis
3.2.4 Ball‐milling Process
3.3 Quantum Confinement Effect
3.3.1 Nanocubes
3.3.2 Nanoplatelets
3.3.3 Nanowires
3.4 Solution‐processed Halide Exchange
3.5 Post‐synthesis Defect Recovery
3.6 Different Shapes of the Nanocrystals
3.6.1 Shape‐controlling Reaction Parameters
3.6.1.1 Temperature
3.6.1.2 Annealing Time
3.6.1.3 Role of Capping‐ligand
3.7 Doping in Perovskite Nanocrystals
3.7.1 Mn2+ Doping
3.7.2 Lanthanide Doping
3.7.3 Other B‐site Dopants
3.7.4 Postsynthesis Doping
3.8 Lead‐free Perovskite Nanocrystals
3.8.1 Classifications According to the Structure and Compositions
3.8.2 Challenges of the Lead‐free Perovskites
3.9 Summary
References
4. Dimensionality Modulation in Halide Perovskites
4.1 Classification of Low‐Dimensional Perovskites
4.1.1 Morphological Low‐Dimensional Perovskites Through Size Reduction (ABX3 Perovskites)
4.1.2 Molecular Low‐Dimensional Perovskites Through Structure Tuning (Non‐ABX3 Perovskites)
4.2 Synthesis and Characterization of Morphological Low‐Dimensional (ABX3) Halide Perovskites
4.2.1 0D Quantum Dots
4.2.2 1D Nanowires
4.2.3 2D Nanoplatelets
4.3 Synthesis and Characterization of Molecular Low‐Dimensional (Non‐ABX3) Halide Perovskites
4.3.1 0D
4.3.1.1 Synthesis and Properties of 0D Perovskites
4.3.1.2 0D Cesium Lead Halides
4.3.2 1D
4.3.3 2D and Quasi‐2D
4.3.3.1 Synthesis of 2D and Quasi‐2D Perovskites Single Crystal
4.3.3.2 Synthesis of 2D and Quasi‐2D Perovskites Nanocrystal
4.4 Applications of Low‐Dimensional Halide Perovskites
4.5 Current Challenges and Prospects of Low‐Dimensional Halide Perovskites
References
5. Halide Double Perovskites
5.1 Definition and Structure
5.2 Properties
5.2.1 Chemical Doping
5.2.2 Random Ordering
5.2.3 Stability
5.3 Applications in Solar Cells and LEDs
5.3.1 Photovoltaic Solar Cells
5.3.2 Light‐Emitting Diodes (LEDs)
5.3.3 White‐LEDs
5.3.4 Phosphorus
5.3.5 Two or More Phosphorus
5.4 Other Applications
5.4.1 Photodetectors
5.4.1.1 UV Detectors
5.4.1.2 X‐Ray Detectors
5.4.2 Memristors
5.4.3 Photocatalysis
5.4.4 Sensors
5.4.5 Future Applications
5.5 Related Materials: Layered Double Perovskites and Vacancy Ordered Double Perovskites
5.5.1 Dimensional Reduction
5.5.2 Vacancy Ordered Perovskites
5.5.2.1 A2B(IV)X6: B(IV) Substitution + Vacancies
5.5.2.2 A3B(III)X9: B(III) Substitution + Vacancies
5.5.2.3 A2B(II)B2(III)X12: B(II), B(III) Substitution + Vacancies □
5.6 Conclusions
References
6. Tin Halide Perovskite Solar Cells
6.1 Introduction
6.2 Tin Perovskite Properties
6.2.1 Crystal Structure
6.2.2 Band Structure and Oxidation
6.2.3 Electrical Properties and Defects
6.3 Perovskite Composition Engineering
6.3.1 Three‐Dimensional TPSC
6.3.2 Low‐Dimensional TPSC
6.4 Additives Manipulation
6.4.1 Crystallization Regulators
6.4.2 Deoxidizers
6.4.3 Interfaces Passivating Materials
6.5 Device Architecture Engineering
6.5.1 Normal and Inverted Structures
6.5.2 Band Alignment
6.6 Conclusion
References
7. Fundamentals and Synthesis Methods of Metal Halide Perovskite Thin Films
7.1 Introduction
7.2 Fundamentals of MHPs Thin Films
7.2.1 Crystal Structures and Compositions
7.2.1.1 3D MHPs
7.2.1.2 Lead‐free MHPs
7.2.1.3 2D MHPs
7.2.2 Microstructures
7.2.2.1 Types of the GBs
7.2.2.2 Grain Size and Distribution
7.2.2.3 Crystallographic Orientations
7.3 Thin Film Growth Mechanism
7.3.1 Crystal Nucleation Mechanism
7.3.1.1 Nucleation Theory
7.3.1.2 Influences on Nucleation
7.3.2 Crystal Growth Mechanism
7.3.2.1 Basic Growth Theory
7.3.2.2 Grain‐coarsening Theory
7.4 One‐step Growth
7.4.1 Growth From Solutions
7.4.1.1 Spin‐coating
7.4.1.2 Drop‐casting
7.4.2 Growth from Vapor Phase
7.4.2.1 Thermal Evaporation
7.4.2.2 Pulsed Laser Deposition
7.5 Two‐step Growth
7.5.1 Growth from Solutions
7.5.1.1 Immersion Method
7.5.1.2 Spin‐coating Method
7.5.1.3 Electro/Chemical Bath Deposition
7.5.2 Growth From Vapor Phase
7.5.2.1 Vapor‐assisted Solution Processing
7.5.2.2 Sequential Vapor Deposition
7.6 Scalable Growth Methods
7.6.1 Blade Coating
7.6.2 Slot‐die Coating
7.6.3 Spray Coating
7.6.4 Meniscus‐assisted Solution Printing
7.6.5 Inkjet Printing
7.7 Postdeposition Treatments
7.7.1 Annealing
7.7.1.1 Solvent Annealing
7.7.1.2 Vacuum‐assisted Annealing
7.7.2 Organic‐gas Dosing
7.8 Summary
Acknowledgments
References
8. First Principles Atomistic Theory of Halide Perovskites
8.1 Introduction: What I Talk About When I Talk About First Principles Calculations of Halide Perovskites
8.2 Structural Properties
8.2.1 A Short Introduction to Density Functional Theory
8.2.2 DFT Calculations in Practice
8.2.2.1 Approximations
8.2.2.2 Calculations of Structural Properties
8.2.3 Zero‐Temperature Calculations for Halide Perovskites
8.2.4 Structural Dynamics
8.2.4.1 Molecular Dynamics: From Classical Force Fields to DFT Accuracy
8.2.4.2 Perovskites and the Breakdown of the Harmonic Approximation
8.2.4.3 A Primer on Ion Migration
8.3 Optoelectronic Properties
8.3.1 Electronic Band Structures
8.3.1.1 What Can DFT Tell Us About Band Gaps of Solids?
8.3.1.2 A Short Introduction to the GW Approach
8.3.1.3 The Band Structure of Halide Perovskites: A Tight‐Binding Perspective
8.3.1.4 Toward Predictive Band Structure Calculations for Halide Perovskites
8.3.2 Optical Properties
8.3.2.1 A Short Introduction to the Bethe–Salpeter Equation Approach
8.3.2.2 Neutral Excitations in Halide Perovskites
8.4 Concluding Remarks: First Person Singular
Acknowledgments
References
9. Comparing the Charge Dynamics in MAPbBr3 and MAPbI3 Using Microwave Photoconductance Measurements
9.1 Time‐Resolved Microwave Conductivity
9.2 Global Modeling of TRMC Data
9.3 TRMC Measurements on MAPbI3 and MAPbBr3
9.4 TRMC Measurements on MAPbI3 and MAPbBr3 with Charge Selective Contacts
Acknowledgement
References
10. Hot Carriers in Halide Perovskites
10.1 Introduction
10.1.1 Potential of Perovskites for Next‐Generation Photovoltaics
10.2 Hot Carrier Cooling Mechanisms
10.3 Slow Hot Carrier Cooling in Halide Perovskites
10.3.1 Hot Phonon Bottleneck
10.3.2 Auger Heating of Hot Carriers
10.3.3 Large Polaron Formation
10.3.4 Spectroscopic Signature of Hot Carriers
10.3.4.1 Transient Absorption
10.3.4.2 Fluorescence‐Based Techniques
10.3.5 Hot Carrier Extraction
10.4 Utilizing Hot Carriers in Halide Perovskites
10.4.1 Hot Carrier Solar Cell
10.4.2 Toward the Realization of Perovskite Hot Carrier Solar Cells
10.4.2.1 Cooling Loss to the Lattice
10.4.2.2 Energy Selective Contacts
10.4.2.3 Loss of Cold Carriers
10.5 Multiple Exciton Generation
10.5.1 MEG Metrics
10.6 Multiple Exciton Generation Mechanisms
10.6.1 The Debate Over the MEG Threshold and MEG Mechanism
10.6.2 Underlying Mechanism of the Efficient MEG in Perovskite
10.6.3 Controversy and Pitfalls Over Photocharging and Artifactual MEG Signal
10.7 Efficient Multiple Exciton Generation in Halide Perovskites
10.7.1 Low Multiple Exciton Generation Threshold
10.7.2 High Multiple Exciton Generation Efficiency
10.7.3 Large Multiple Exciton Generation Quantum Yield
10.7.4 Spectroscopic Signatures of Multiple Exciton Generation
10.7.4.1 Transient Absorption Spectroscopy
10.7.4.2 Photocurrent‐Based Techniques
10.8 Utilizing Multiple Exciton Generation in Halide Perovskites
10.8.1 Multiple Exciton Generation Solar Cells
10.8.2 Potential of Multiple Exciton Generation Solar cells
10.9 Conclusion and Outlook
References
11. Ionic Transport in Perovskite Semiconductors
11.1 Theoretical Basis of Ionic Transport
11.2 Characterizations of Ionic Transport
11.3 Mobile Ions in Perovskite Film Under Electric Field
11.4 The Factors Affecting Ionic Transport in Perovskites
11.4.1 Moisture
11.4.2 Light Illumination
11.4.3 Perovskite Composition
11.4.4 Grain Boundary
11.4.5 Lattice Strain
11.5 The Impact of Ionic Transport on Perovskite Films and Devices
11.5.1 Phase Segregation
11.5.2 Doping Effects
11.5.3 SCLC and TFT Devices
11.5.4 Degradation in Functional Devices
11.6 Summary and Outlook
References
12. Light Emission of Halide Perovskites
12.1 Introduction
12.2 Charge‐Carrier Recombination in Lead‐Halide Perovskites
12.2.1 Monomolecular Recombination
12.2.2 Bimolecular Recombination
12.2.3 Trimolecular Recombination
12.2.4 Recombination Constants in Excitonic Systems
12.2.5 Common Recombination Dynamics Measurement Techniques and Experimental Evidence
12.3 Photoinduced Effects on Charge Carrier Recombination
12.4 Lasing in Lead‐Halide Perovskites
12.5 Conclusions
References
13. Epitaxy and Strain Engineering of Halide Perovskites
13.1 Introduction
13.2 Epitaxy of Thin Film and Nanostructures
13.2.1 Epitaxial Substrates
13.2.2 Epitaxial Growth and Defects Formation Mechanisms
13.2.3 Experimental Progresses
13.3 Strain Engineering
13.3.1 Theoretical Progresses
13.3.2 Experimental Progresses
13.4 Opportunities and Challenges
Acknowledgments
References
14. Electron Microscopy of Perovskite Solar Cell Materials
14.1 Introduction
14.2 Fundamentals of Electron Microscopy
14.3 Signal Generation
14.4 SEM
14.4.1 Cathodoluminescence
14.4.1.1 Comparison of CL and Photoluminescence (PL)
14.4.1.2 Working Principle
14.4.1.3 CL for Perovskites
14.4.2 Electron‐Beam‐Induced Current
14.4.2.1 Working Principle of EBIC
14.4.2.2 Applications
14.4.3 Electron Backscatter Diffraction
14.4.3.1 Differences Between EBSD, XRD, and TEM
14.4.3.2 Working Principle of EBSD
14.4.3.3 EBSD for Perovskites
14.4.4 TEM
14.4.4.1 Sample Preparation and Transfer
14.4.4.2 Imaging Conditions
14.4.4.3 Beam Damage
14.4.4.4 Examples of Applications of TEM
14.5 Conclusions
Acknowledgments
References
15. In Situ Characterization of Halide Perovskite Synthesis
15.1 Introduction
15.2 Fundamentals of X‐Ray Scattering and Fluorescence Techniques
15.2.1 Grazing Incidence Wide‐Angle X‐Ray Scattering (GIWAXS)
15.2.2 Grazing Incidence Small‐Angle X‐Ray Scattering (GISAXS)
15.2.3 X‐Ray Fluorescence (XRF)
15.2.4 Selected Examples for In Situ X‐Ray Scattering and Fluorescence
15.2.4.1 In Situ GIWAXS to Study Crystallization Kinetics and A‐Site Doping
15.2.4.2 In Situ GIWAXS to Probe Film Evolution via Antisolvent and Gas Jet Treatments
15.2.4.3 In Situ X‐Ray Diffraction (XRD), XRF, and GISAXS to Probe the PbCl2‐Derived Formation of MAPbI3
15.2.4.4 In Situ GIWAXS to Probe the 2D Perovskite Formation on 3D Films
15.3 In Situ Optical Spectroscopy
15.3.1 Fundamentals of Absorption and Emission of Light in Halide Perovskites
15.3.2 Setup Design for In Situ Optical Spectroscopy
15.3.3 Selected Examples for In Situ Optical Spectroscopy
15.3.3.1 Fast In Situ Reflectance Measurements to Characterize the Perovskite Formation
15.3.3.2 In Situ UV–Vis Absorbance Characterization During the Drying Stage
15.3.3.3 In Situ Photoluminescence Characterization to Investigate the Role of the Precursor
15.4 Examples of In Situ Multimodal Characterization During Solution‐Based Fabrication
15.5 Probing Beam–Sample Interaction
15.6 Summary and Outlook
Acknowledgments
References
16. Multimodal Characterization of Halide Perovskites: From the Macro to the Atomic Scale
16.1 Introduction
16.2 Early Multimodal Characterization Work
16.3 Recent Multimodal Characterization
16.3.1 Subgrain Features
16.3.2 Strain and Photophysics
16.3.3 Atomic Scale Multimodal Studies
16.4 Pressing Challenges and Opportunities
16.4.1 Challenges: Beam Damage
16.4.2 Challenges: Resolution Limits
16.4.3 Challenges: Image Registration and Sample Fabrication
16.4.4 Challenges: Facility Access and Data Acquisition
16.5 Outlook and Opportunities
References
Index