Hybrid Organic-Inorganic Perovskites

Wei Li is a Professor of School of Materials Science and Engineering at Nankai University. His research interests include the synthesis and physical properties of hybrid crystals (especially hybrid organic-inorganic perovskites and metal-organic frameworks), and their potential applications in energy and optoelectronics. Alessandro Stroppa is a senior researcher of the National Research Council (CNR), SPIN Institute in Italy. Since 2019, he is deputy director of the CNR-SPIN unit in L'Aquila. His current research focuses on the solid-state physics and material science. He has published more than 110 peer-viewed papers (h-index 33) and received several honors including selection of one of his articles for the 'Best 2008 New Journal of Physics Collection', Research Highlight talk at EUROMAT 2013, and Certificate of Appreciation for his theoretical studies on multiferroic metal-organic frameworks at Nature Conference (Tianjin, 2019). Zhe-Ming Wang is a professor of College of Chemistry and Molecular Engineering at Peking University. His current research interest covers functional coordination compounds, crystal engineering, molecule-based magnetic and dielectric materials, especially, the functional materials of metal formates. He has published more than 100 papers with other authors. Song Gao is a Professor of South China University of Technology and Peking University. He was elected to CAS in 2007, and TWAS in 2013. He is the editor-in-chief of Inorg. Chem. Front. and an associate editor of Nat. Sci. Rev. He was the vice president and provost of Peking University from 2013 to 2018, and currently the president of South China University of Technology. His research focuses on coordination chemistry and molecule-based magnets.

• Preface ixAcknowledgements xi1 Introduction to Hybrid Organic–Inorganic Perovskites 11.1 Perovskite Oxides 11.2 Evolution from Perovskite Oxides to Hybrid Organic–Inorganic Perovskites 31.3 Classification and Chemical Variations of HOIPs 41.4 Structure, Symmetry, and Property Features of HOIPs 51.4.1 General Trend 51.4.2 Ion Radius Matchability and Tolerance Factor 71.4.3 Phase Transitions 10References 122 Hybrid Halide Perovskites 152.1 Synthesis and Chemical Diversity 152.2 Symmetries and Structures 192.3 Phase Transitions 242.4 Physical Properties 292.4.1 Semiconductivity and Bandgap Structures 292.4.2 Transport Properties and Photovoltaics 322.4.3 Laser Physics 492.4.4 Light-Emitting Diodes 542.4.5 Photodetectors 592.4.6 Ferroelectricity and Rashba Effect 632.4.7 Mechanical Properties 662.4.8 Thermal Conductivity 702.4.9 Caloric Effects 712.4.10 Other Properties and Applications 73References 733 Hybrid Formate Perovskites 793.1 Synthesis and Chemical Diversity 793.2 Symmetries and Structures 823.3 Phase Transitions and Order–Disorder 913.4 Physical Properties 943.4.1 Magnetism 943.4.1.1 Spin-Canting and JT Effect 943.4.1.2 Spin-Flop 983.4.1.3 Quantum Tunnelling 1013.4.2 Dielectricity 1023.4.3 Ferroelectricity 1053.4.4 Ferroelasticity 1143.4.5 Multiferroicity 1183.4.6 Mechanical Properties 1253.4.7 Thermal Expansion 1343.4.8 Caloric Effects 139References 1454 Hybrid Azide Perovskites 1514.1 Synthesis and Structures 1514.2 Phase Transitions 1564.3 Physical Properties 1644.3.1 Magnetism 1644.3.2 Dielectricity 1674.3.3 Anti-ferroelectricity and Ferroelasticity 1744.3.4 Thermal Expansion 1764.3.5 Mechanical Properties 177References 1785 Hybrid Dicyanamide Perovskites 1815.1 Synthesis and Structures 1815.2 Phase Transitions 1855.3 Physical Properties 1885.3.1 Dielectricity 1885.3.2 Optical Properties and Second Harmonic Generation (SHG) Effects 1905.3.3 Magnetism 1915.3.4 Mechanical Properties and Thermal Expansion 1935.3.5 Caloric Effects 195References 1976 Hybrid Cyanide Perovskites 1996.1 Synthesis and Structures 1996.2 Phase Transitions (PT) 2046.3 Physical Properties 2116.3.1 Second Harmonic Generation (SHG) 2116.3.2 Dielectricity 2116.3.3 Ferroelectricity 215References 2177 Hybrid Dicyanometallate and Borohydride Perovskites 2197.1 Hybrid Dicyanometallate Perovskites 2197.1.1 Synthesis, Structures, and Phase Transitions 2197.1.2 Physical Properties 2227.2 Hybrid Borohydride Perovskites 223References 2238 Hybrid Hypophosphite Perovskites 2258.1 Synthesis 2258.2 Symmetries and Structures 2278.3 Phase Transitions 2298.4 Physical Properties 2318.4.1 Mechanical Properties 2318.4.2 Magnetism 231References 2339 Other Perovskite-Like Hybrid Materials and Metal-Free Perovskites 2359.1 Hybrid Organic–Inorganic Perchlorates 2359.1.1 Synthesis, Structures, and Phase Transitions 2359.1.2 Physical Properties 2399.1.2.1 Mechanical Properties 2409.1.2.2 Dielectric Properties 2439.1.2.3 High Energetic Properties 2449.2 Hybrid Organic–Inorganic Tetrafluoroborates 2469.2.1 Synthesis, Structures, and Phase Transitions 2469.2.2 Physical Properties 2489.3 Metal-Free Perovskites 2499.3.1 Synthesis, Structures, and Electronic Properties 2499.3.2 Phase Transitions 2559.3.3 Physical Properties 2559.3.3.1 Photoluminescence 2559.3.3.2 Ferroelectricity and Dielectricity 2569.3.3.3 Mechanical Properties 260References 26510 Concluding Remarks and Future Perspectives 267Index 271