Perovskites

Richard J. D. Tilley, D. Sc, Ph. D, is Emeritus Professor in the School of Engineering at the University of Cardiff, Wales, U.K. He has published extensively in the area of solid-state materials science, including four books for Wiley, 180 papers, and 15 fifteen book chapters.

• Preface xi1 The ABX3 Perovskite Structure 11.1 Perovskites 11.2 The Cubic Perovskite Structure: SrTiO3 41.3 The Goldschmidt Tolerance Factor 61.4 ABX3 Perovskite Structure Variants 111.5 Cation Displacement: BaTiO3 as an Example 121.6 Jahn–Teller Octahedral Distortion: KCuF3 as an Example 161.7 Octahedral Tilting 191.7.1 Tilt Descriptions 191.7.2 Trigonal Symmetry: LaAlO3 as an Example 241.7.3 Orthorhombic Symmetry: GdFeO3 and CaTiO3 as Examples 261.8 Symmetry Relationships 301.9 Hybrid Organic–Inorganic Perovskites 331.10 Antiperovskites 341.10.1 Cubic and Related Structures 341.10.2 Other Structures 361.11 Structure‐Field Maps 361.12 Theoretical Calculations 38References 40Further Reading 402 ABX3–Related Structures 422.1 Double Perovskites and Related Ordered Structures 422.1.1 Rock‐Salt Ordered Double Perovskites 422.1.2 Other Ordered Perovskites 452.1.3 AA′3B4O12‐Related Phases 482.2 Anion Substituted Perovskites 512.2.1 Nitrides and Oxynitrides 512.2.2 Oxyfluorides 532.3 A‐Site‐Deficient Perovskite Structures 542.3.1 ReO3, WO3 and Related Structures 542.3.2 Perovskite Tungsten Bronzes 552.3.3 A‐Site‐Deficient Titanates, Niobates and Tantalates 552.4 Anion‐Deficient Phases Containing Tetrahedra 572.4.1 Brownmillerites 572.4.2 Brownmillerite Microstructures 622.4.3 Temperature Variation and Disorder 632.4.4 B‐Site Doped Brownmillerite Phases 642.4.5 B‐Site Doping and Oxygen Pressure 652.4.6 A‐Site Doped Brownmillerite Phases 652.4.7 Brownmillerite‐Related Phases 662.5 Anion‐Deficient Phases Containing Square Pyramids 692.5.1 Manganites 692.5.2 SrFeO2.5 and Related Phases 712.5.3 Cobaltite‐Related Phases 732.6 Point Defects, Microdomains and Modulated Phases 74Further Reading 783 Hexagonal Perovskite–Related Structures 793.1 The BaNiO3 Structure 793.2 BaNiO3‐Related Phases Containing Trigonal Prisms 813.2.1 Commensurate Structures 813.2.2 Modulated Structures 893.3 Perovskites with Mixed Hexagonal/Cubic Packing: Nomenclature 923.4 Perovskites with Mixed Hexagonal/Cubic Packing: Stacking Sequences 953.5 Hexagonal Perovskites with chq and cph Stacking 983.5.1 (chq) Structures 983.5.2 (cph) Structures 993.5.3 cphq Intergrowth Structures 1043.6 Hexagonal Perovskites with cphh Stacking 1063.6.1 (cc…chh) AnBnO3n Structures 1073.6.2 (cc…chh) AnBn−1O3n Structures 1083.6.3 (hhcc…chhcc…c) Intergrowth Phases 1103.6.4 (cc…ch) AnBn−1O3n Shift and Twinned Phases 1123.7 Anion‐Deficient Phases Containing BaO2 (c′) Layers 1123.7.1 (c…c′…ch) Structures 1133.7.2 (c…c′…chh) Structures 1133.7.3 (c…c′…chhh) Structures 1153.8 Anion‐Deficient Phases with BaOX Layers 1173.8.1 (h′) Layers 1173.8.2 (c′c′) Layers 1193.9 Sr4Mn3O10 and Ba6Mn5O16 1203.10 Temperature and Pressure Variation 120Reference 122Further Reading 1224 Modular Structures 1234.1 K2NiF4 (A2BX4) and Ruddlesden–Popper Phases 1234.1.1 The K2NiF4 (T or T/O) Structure 1234.1.2 Ruddlesden–Popper Phases 1274.2 The Nd2CuO4 (T′) and T* Structures 1294.3 Dion–Jacobson and Related Phases 1314.4 Aurivillius Phases 1344.5 The Ca2Nb2O7‐Related Phases 1364.6 Cuprate Superconductors and Related Phases 1384.6.1 La2CuO4, Nd2CuO4 and YBa2Cu3O7 1394.6.2 Layered Perovskite Structures 1414.6.3 Structures Related to the Layered Cuprate Phases 1424.7 Composition Variation 1464.8 Intercalation and Exfoliation 151Further Reading 1545 Diffusion and Ionic Conductivity 1565.1 Diffusion 1565.2 Ionic Conductivity 1595.3 Proton Conductivity 1625.4 Oxygen Pressure Dependence and Electronic Conductivity 1655.5 Oxide Ion Mixed Conductors 1675.6 Proton Mixed Conductors 1695.7 Solid Oxide Fuel Cells 172References 174Further Reading 1746 Dielectric Properties 1766.1 Insulating Perovskites 1766.2 Dielectric Perovskites 1786.2.1 General Properties 1786.2.2 Colossal Dielectric Constant Materials 1816.3 Ferroelectric/Piezoelectric Perovskites 1826.3.1 Spontaneous Polarisation and Domains 1826.3.2 Ferroelectric Domain Switching 1856.3.3 Ferroelectric Hysteresis Loops 1886.3.4 Temperature Dependence of Ferroelectricity 1896.3.5 Pyroelectrics, Piezoelectrics and Crystal Symmetry 1916.3.6 Strain versus Electric Field Loops 1926.4 The Development of Ferroelectric/Piezoelectric Ceramic Bodies 1936.4.1 Ceramic Piezoelectrics 1936.4.2 Electrostriction 1956.5 Antiferroelectrics 1966.6 Ferrielectrics 1996.7 Relaxor Ferroelectrics 2006.7.1 Macroscopic Characteristics of Relaxor Ferroelectrics 2006.7.2 Microstructures of Relaxor Ferroelectrics 2026.8 Improper Ferroelectricity 2066.9 Doping and Modification of Properties 2086.10 Nanoparticles and Thin Films 212References 215Further Reading 2157 Magnetic Properties 2177.1 Magnetism in Perovskites 2177.2 Paramagnetic Perovskites 2197.3 Antiferromagnetic Perovskites 2227.3.1 Cubic Perovskite‐Related Structures 2227.3.2 Hexagonal Perovskites 2297.4 Ferromagnetic Perovskites 2337.5 Ferrimagnetic Perovskites 2367.6 Spin Glass Behaviour 2377.7 Canted Spins and Other Magnetic Ordering 2387.8 Thin Films 2407.9 Nanoparticles 2437.10 Multiferroic Perovskites 243References 246Further Reading 2468 Electronic Conductivity 2478.1 Perovskite Band Structure: Metallic Perovskites 2478.2 Metal–Insulator Transitions 2508.2.1 Titanates and Related Phases 2508.2.2 LnNiO3 2528.2.3 Lanthanoid Manganites 2538.2.4 Lanthanoid Cobaltites 2548.2.5 (Sr, Ca)2RuO4 and Ca2Ru1−xCrxO4 2558.2.6 NaOsO3 2568.3 Perovskite Superconductors 2578.4 Cuprate High‐Temperature Superconductors 2588.4.1 Overview 2588.4.2 Lanthanum Cuprate, La2CuO4 2598.4.3 Neodymium Cuprate, Nd2CuO4 2608.4.4 Yttrium Barium Copper Oxide, YBa2Cu3O7 2618.4.5 Perovskite‐Related Structures and Series 2638.4.6 The Generic Superconductivity Phase Diagram 2638.4.7 Defects and Conductivity 2658.5 Spin Polarisation and Half‐Metals 2678.6 Charge Ordering and Orbital Ordering 2688.7 Magnetoresistance 2708.7.1 Collosal Magnetoresistance (CMR) in Manganites 2708.7.2 Low‐Field Magnetoresistance 2728.8 Semiconductivity in Perovskites 2728.9 Thin Films and Surface Conductivity 275References 275Further Reading 2759 Thermal and Optical Properties 2779.1 Thermal Expansion 2779.1.1 Normal Thermal Expansion 2779.1.2 Thermal Contraction 2809.1.3 Zero Thermal Expansion Materials 2839.2 Thermoelectric Properties 2849.3 The Magnetocaloric Effect 2879.4 The Pyroelectric and Electrocaloric Effect 2889.5 Transparency 2899.6 Electrochromic Films 2919.7 Electro‐optic Properties 2939.7.1 Refractive Index Changes 2939.7.2 Electro‐optic Phase Modulators 2949.7.3 Electro‐optic Intensity Modulators 2969.7.4 Ceramic Modulators 2999.8 Perovskite Solar Cells 299Reference 302Further Reading 302Appendix A The Bond Valence Model for Perovskites 303Appendix B Summary of the Kröger–Vink Defect Notation 307Index 309