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Hybrid organic-inorganic perovskites (HOIPs) have attracted substantial interest due to their chemical variability, structural diversity and favorable physical properties the past decade. This materials class encompasses other important families such as formates, azides, dicyanamides, cyanides and dicyanometallates.
 
The book summarizes the chemical variability and structural diversity of all known hybrid organic-inorganic perovskites subclasses including halides, azides, formates, dicyanamides, cyanides and dicyanometallates. It also presents a comprehensive account of their intriguing physical properties, including photovoltaic, optoelectronic, dielectric, magnetic, ferroelectric, ferroelastic and multiferroic properties. Moreover, the current challenges and future opportunities in this exciting field are also been discussed. This timely book shows the readers a complete landscape of hybrid organic-inorganic pervoskites and associated multifuctionalities.

Hybrid Organic-Inorganic Perovskites

Preface ix





Acknowledgements xi





1 Introduction to Hybrid Organic-Inorganic Perovskites 1





1.1 Perovskite Oxides 1





1.2 Evolution from Perovskite Oxides to Hybrid Organic-Inorganic Perovskites 3





1.3 Classification and Chemical Variations of HOIPs 4





1.4 Structure, Symmetry, and Property Features of HOIPs 5





1.4.1 General Trend 5





1.4.2 Ion Radius Matchability and Tolerance Factor 7





1.4.3 Phase Transitions 10





References 12





2 Hybrid Halide Perovskites 15





2.1 Synthesis and Chemical Diversity 15





2.2 Symmetries and Structures 19





2.3 Phase Transitions 24





2.4 Physical Properties 29





2.4.1 Semiconductivity and Bandgap Structures 29





2.4.2 Transport Properties and Photovoltaics 32





2.4.3 Laser Physics 49





2.4.4 Light-Emitting Diodes 54





2.4.5 Photodetectors 59





2.4.6 Ferroelectricity and Rashba Effect 63





2.4.7 Mechanical Properties 66





2.4.8 Thermal Conductivity 70





2.4.9 Caloric Effects 71





2.4.10 Other Properties and Applications 73





References 73





3 Hybrid Formate Perovskites 79





3.1 Synthesis and Chemical Diversity 79





3.2 Symmetries and Structures 82





3.3 Phase Transitions and Order-Disorder 91





3.4 Physical Properties 94





3.4.1 Magnetism 94





3.4.1.1 Spin-Canting and JT Effect 94





3.4.1.2 Spin-Flop 98





3.4.1.3 Quantum Tunnelling 101





3.4.2 Dielectricity 102





3.4.3 Ferroelectricity 105





3.4.4 Ferroelasticity 114





3.4.5 Multiferroicity 118





3.4.6 Mechanical Properties 125





3.4.7 Thermal Expansion 134





3.4.8 Caloric Effects 139





References 145





4 Hybrid Azide Perovskites 151





4.1 Synthesis and Structures 151





4.2 Phase Transitions 156





4.3 Physical Properties 164





4.3.1 Magnetism 164





4.3.2 Dielectricity 167





4.3.3 Anti-ferroelectricity and Ferroelasticity 174





4.3.4 Thermal Expansion 176





4.3.5 Mechanical Properties 177





References 178





5 Hybrid Dicyanamide Perovskites 181





5.1 Synthesis and Structures 181





5.2 Phase Transitions 185





5.3 Physical Properties 188





5.3.1 Dielectricity 188





5.3.2 Optical Properties and Second Harmonic Generation (SHG) Effects 190





5.3.3 Magnetism 191





5.3.4 Mechanical Properties and Thermal Expansion 193





5.3.5 Caloric Effects 195





References 197





6 Hybrid Cyanide Perovskites 199





6.1 Synthesis and Structures 199





6.2 Phase Transitions (PT) 204





6.3 Physical Properties 211





6.3.1 Second Harmonic Generation (SHG) 211





6.3.2 Dielectricity 211





6.3.3 Ferroelectricity 215





References 217





7 Hybrid Dicyanometallate and Borohydride Perovskites 219





7.1 Hybrid Dicyanometallate Perovskites 219





7.1.1 Synthesis, Structures, and Phase Transitions 219





7.1.2 Physical Properties 222





7.2 Hybrid Borohydride Perovskites 223





References 223





8 Hybrid Hypophosphite Perovskites 225





8.1 Synthesis 225





8.2 Symmetries and Structures 227





8.3 Phase Transitions 229





8.4 Physical Properties 231





8.4.1 Mechanical Properties 231





8.4.2 Magnetism 231





References 233





9 Other Perovskite-Like Hybrid Materials and Metal-Free Perovskites 235





9.1 Hybrid Organic-Inorganic Perchlorates 235





9.1.1 Synthesis, Structures, and Phase Transitions 235





9.1.2 Physical Properties 239





9.1.2.1 Mechanical Properties 240





9.1.2.2 Dielectric Properties 243





9.1.2.3 High Energetic Properties 244





9.2 Hybrid Organic-Inorganic Tetrafluoroborates 246





9.2.1 Synthesis, Structures, and Phase Transitions 246





9.2.2 Physical Properties 248





9.3 Metal-Free Perovskites 249





9.3.1 Synthesis, Structures, and Electronic Properties 249





9.3.2 Phase Transitions 255





9.3.3 Physical Properties 255





9.3.3.1 Photoluminescence 255





9.3.3.2 Ferroelectricity and Dielectricity 256





9.3.3.3 Mechanical Properties 260





References 265





10 Concluding Remarks and Future Perspectives 267





Index 271