Professor Duncan Bruce graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. Dr. Richard Walton, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.Dermot O'Hare is Professor in the Chemistry Research Laboratory at the University of Oxford.His research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids.Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Noncentrosymmetric Inorganic Oxide Materials: Synthetic Strategies and Characterisation Techniques 1P. Shiv Halasyamani1.1 Introduction 11.2 Strategies toward Synthesising Noncentrosymmetric Inorganic Materials 31.3 Electronic Distortions 41.3.1 Metal Oxyfluoride Systems 81.3.2 Salt-Inclusion Solids 91.3.3 Borates 111.3.4 Noncentrosymmetric Coordination Networks 121.4 Properties Associated with Noncentrosymmetric Materials 161.4.1 Second-Harmonic Generation 181.4.2 Piezoelectricity 211.4.3 Pyroelectricity 251.4.4 Ferroelectricity 271.5 Outlook – Multifunctional Materials 301.5.1 Perovskites 311.5.2 Hexagonal Manganites 321.5.3 Metal Halide and Oxy-Halide Systems 321.6 Concluding Thoughts 331.6.1 State of the Field 33Acknowledgements 34References 342 Geometrically Frustrated Magnetic Materials 41John E. Greedan2.1 Introduction 412.2 Geometric Frustration 422.2.1 Definition and Criteria: Subversion of the Third Law 422.2.2 Magnetism Short Course 432.2.3 Frustrated Lattices – The Big Four 462.2.4 Ground States of Frustrated Systems: Consequences of Macroscopic Degeneracy 462.3 Real Materials 522.3.1 The Triangular Planar (TP) Lattice 522.3.2 The Kagome´ Lattice 572.3.3 The Face-Centred Cubic Lattice 722.3.4 The Pyrochlores and Spinels 762.3.5 Other Frustrated Lattices 1052.4 Concluding Remarks 108References 1093 Lithium Ion Conduction in Oxides 119Edmund Cussen3.1 Introduction 1193.2 Sodium and Lithium b-Alumina 1263.3 Akali Metal Sulfates and the Effect of Anion Disorder on Conductivity 1323.4 LISICON and Related Phases 1453.5 Lithium Conduction in NASICON-Related Phases 1553.6 Doped Analogues of LiZr2(PO4)3 1643.7 Lithium Conduction in the Perovskite Structure 1753.7.1 The Structures of Li3xLa2/3xTiO3 1813.7.2 Doping Studies of Lithium Perovskites 1853.8 Lithium-Containing Garnets 187References 1974 Thermoelectric Oxides 203Sylvie Hébert and Antoine Maignan4.1 Introduction 2034.2 How to Optimise Thermoelectric Generators (TEG) 2044.2.1 Principle of a TEG 2044.2.2 The Figure of Merit 2074.2.3 Beyond the Classical Approach 2104.3 Thermoelectric Oxides 2134.3.1 Semiconducting Oxides and the Heikes Formula 2154.3.2 NaxCoO2 and the Misfit Cobaltate Family 2214.3.3 Degenerate Semiconductors 2404.3.4 All-Oxide Modules 2494.4 Conclusion 251Acknowledgements 252References 2525 Transition Metal Oxides: Magnetoresistance and Half-Metallicity 257Tapas Kumar Mandal and Martha Greenblatt5.1 Introduction 2575.2 Magnetoresistance: Concepts and Development 2585.2.1 Phenomenon of Magnetoresistance: Metallic Multilayers and Anisotropic Magnetoresistance (AMR) 2585.2.2 Giant Magnetoresistance (GMR) Effect 2595.2.3 Colossal Magnetoresistance (CMR) in Perovskite Oxomanganates 2615.2.4 Tunnelling Magnetoresistance (TMR) and Magnetic Tunnel Junctions (MTJ) 2635.2.5 Powder, Intrinsic and Extrinsic MR 2635.3 Half-Metallicity 2645.3.1 Half-Metallicity in Heusler Alloys 2645.3.2 Half-Metallic Ferro/Ferrimagnets, Antiferromagnets 2655.4 Oxides Exhibiting Half-Metallicity 2665.4.1 CrO2 2665.4.2 Fe3O4 and Other Spinel Oxides 2685.4.3 Perovskite Oxomanganates 2705.4.4 Double Perovskites 2725.5 Magnetoresistance and Half-Metallicity of Double Perovskites 2735.5.1 Double Perovskite Structure 2735.5.2 Ordering and Anti-Site (AS) Disorder in Double Perovskites 2765.5.3 Electronic Structure and Magnetic Properties of Double Perovskites 2815.5.4 Magnetoresistance and Half-Metallicity in Double Perovskites 2845.5.5 High Curie Temperature (TC) Double Perovskites and Room Temperature MR 2855.6 Spintronics – The Emerging Magneto-Electronics 2865.7 Summary 288Acknowledgements 289References 289Index 295

Professor Duncan Bruce graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. Dr. Richard Walton, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.Dermot O'Hare is Professor in the Chemistry Research Laboratory at the University of Oxford.His research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids.Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Noncentrosymmetric Inorganic Oxide Materials: Synthetic Strategies and Characterisation Techniques 1P. Shiv Halasyamani1.1 Introduction 11.2 Strategies toward Synthesising Noncentrosymmetric Inorganic Materials 31.3 Electronic Distortions 41.3.1 Metal Oxyfluoride Systems 81.3.2 Salt-Inclusion Solids 91.3.3 Borates 111.3.4 Noncentrosymmetric Coordination Networks 121.4 Properties Associated with Noncentrosymmetric Materials 161.4.1 Second-Harmonic Generation 181.4.2 Piezoelectricity 211.4.3 Pyroelectricity 251.4.4 Ferroelectricity 271.5 Outlook – Multifunctional Materials 301.5.1 Perovskites 311.5.2 Hexagonal Manganites 321.5.3 Metal Halide and Oxy-Halide Systems 321.6 Concluding Thoughts 331.6.1 State of the Field 33Acknowledgements 34References 342 Geometrically Frustrated Magnetic Materials 41John E. Greedan2.1 Introduction 412.2 Geometric Frustration 422.2.1 Definition and Criteria: Subversion of the Third Law 422.2.2 Magnetism Short Course 432.2.3 Frustrated Lattices – The Big Four 462.2.4 Ground States of Frustrated Systems: Consequences of Macroscopic Degeneracy 462.3 Real Materials 522.3.1 The Triangular Planar (TP) Lattice 522.3.2 The Kagome´ Lattice 572.3.3 The Face-Centred Cubic Lattice 722.3.4 The Pyrochlores and Spinels 762.3.5 Other Frustrated Lattices 1052.4 Concluding Remarks 108References 1093 Lithium Ion Conduction in Oxides 119Edmund Cussen3.1 Introduction 1193.2 Sodium and Lithium b-Alumina 1263.3 Akali Metal Sulfates and the Effect of Anion Disorder on Conductivity 1323.4 LISICON and Related Phases 1453.5 Lithium Conduction in NASICON-Related Phases 1553.6 Doped Analogues of LiZr2(PO4)3 1643.7 Lithium Conduction in the Perovskite Structure 1753.7.1 The Structures of Li3xLa2/3xTiO3 1813.7.2 Doping Studies of Lithium Perovskites 1853.8 Lithium-Containing Garnets 187References 1974 Thermoelectric Oxides 203Sylvie Hébert and Antoine Maignan4.1 Introduction 2034.2 How to Optimise Thermoelectric Generators (TEG) 2044.2.1 Principle of a TEG 2044.2.2 The Figure of Merit 2074.2.3 Beyond the Classical Approach 2104.3 Thermoelectric Oxides 2134.3.1 Semiconducting Oxides and the Heikes Formula 2154.3.2 NaxCoO2 and the Misfit Cobaltate Family 2214.3.3 Degenerate Semiconductors 2404.3.4 All-Oxide Modules 2494.4 Conclusion 251Acknowledgements 252References 2525 Transition Metal Oxides: Magnetoresistance and Half-Metallicity 257Tapas Kumar Mandal and Martha Greenblatt5.1 Introduction 2575.2 Magnetoresistance: Concepts and Development 2585.2.1 Phenomenon of Magnetoresistance: Metallic Multilayers and Anisotropic Magnetoresistance (AMR) 2585.2.2 Giant Magnetoresistance (GMR) Effect 2595.2.3 Colossal Magnetoresistance (CMR) in Perovskite Oxomanganates 2615.2.4 Tunnelling Magnetoresistance (TMR) and Magnetic Tunnel Junctions (MTJ) 2635.2.5 Powder, Intrinsic and Extrinsic MR 2635.3 Half-Metallicity 2645.3.1 Half-Metallicity in Heusler Alloys 2645.3.2 Half-Metallic Ferro/Ferrimagnets, Antiferromagnets 2655.4 Oxides Exhibiting Half-Metallicity 2665.4.1 CrO2 2665.4.2 Fe3O4 and Other Spinel Oxides 2685.4.3 Perovskite Oxomanganates 2705.4.4 Double Perovskites 2725.5 Magnetoresistance and Half-Metallicity of Double Perovskites 2735.5.1 Double Perovskite Structure 2735.5.2 Ordering and Anti-Site (AS) Disorder in Double Perovskites 2765.5.3 Electronic Structure and Magnetic Properties of Double Perovskites 2815.5.4 Magnetoresistance and Half-Metallicity in Double Perovskites 2845.5.5 High Curie Temperature (TC) Double Perovskites and Room Temperature MR 2855.6 Spintronics – The Emerging Magneto-Electronics 2865.7 Summary 288Acknowledgements 289References 289Index 295

Professor Duncan Bruce graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. Dr. Richard Walton, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.Dermot O'Hare is Professor in the Chemistry Research Laboratory at the University of Oxford.His research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids.Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Noncentrosymmetric Inorganic Oxide Materials: Synthetic Strategies and Characterisation Techniques 1P. Shiv Halasyamani1.1 Introduction 11.2 Strategies toward Synthesising Noncentrosymmetric Inorganic Materials 31.3 Electronic Distortions 41.3.1 Metal Oxyfluoride Systems 81.3.2 Salt-Inclusion Solids 91.3.3 Borates 111.3.4 Noncentrosymmetric Coordination Networks 121.4 Properties Associated with Noncentrosymmetric Materials 161.4.1 Second-Harmonic Generation 181.4.2 Piezoelectricity 211.4.3 Pyroelectricity 251.4.4 Ferroelectricity 271.5 Outlook – Multifunctional Materials 301.5.1 Perovskites 311.5.2 Hexagonal Manganites 321.5.3 Metal Halide and Oxy-Halide Systems 321.6 Concluding Thoughts 331.6.1 State of the Field 33Acknowledgements 34References 342 Geometrically Frustrated Magnetic Materials 41John E. Greedan2.1 Introduction 412.2 Geometric Frustration 422.2.1 Definition and Criteria: Subversion of the Third Law 422.2.2 Magnetism Short Course 432.2.3 Frustrated Lattices – The Big Four 462.2.4 Ground States of Frustrated Systems: Consequences of Macroscopic Degeneracy 462.3 Real Materials 522.3.1 The Triangular Planar (TP) Lattice 522.3.2 The Kagome´ Lattice 572.3.3 The Face-Centred Cubic Lattice 722.3.4 The Pyrochlores and Spinels 762.3.5 Other Frustrated Lattices 1052.4 Concluding Remarks 108References 1093 Lithium Ion Conduction in Oxides 119Edmund Cussen3.1 Introduction 1193.2 Sodium and Lithium b-Alumina 1263.3 Akali Metal Sulfates and the Effect of Anion Disorder on Conductivity 1323.4 LISICON and Related Phases 1453.5 Lithium Conduction in NASICON-Related Phases 1553.6 Doped Analogues of LiZr2(PO4)3 1643.7 Lithium Conduction in the Perovskite Structure 1753.7.1 The Structures of Li3xLa2/3xTiO3 1813.7.2 Doping Studies of Lithium Perovskites 1853.8 Lithium-Containing Garnets 187References 1974 Thermoelectric Oxides 203Sylvie Hébert and Antoine Maignan4.1 Introduction 2034.2 How to Optimise Thermoelectric Generators (TEG) 2044.2.1 Principle of a TEG 2044.2.2 The Figure of Merit 2074.2.3 Beyond the Classical Approach 2104.3 Thermoelectric Oxides 2134.3.1 Semiconducting Oxides and the Heikes Formula 2154.3.2 NaxCoO2 and the Misfit Cobaltate Family 2214.3.3 Degenerate Semiconductors 2404.3.4 All-Oxide Modules 2494.4 Conclusion 251Acknowledgements 252References 2525 Transition Metal Oxides: Magnetoresistance and Half-Metallicity 257Tapas Kumar Mandal and Martha Greenblatt5.1 Introduction 2575.2 Magnetoresistance: Concepts and Development 2585.2.1 Phenomenon of Magnetoresistance: Metallic Multilayers and Anisotropic Magnetoresistance (AMR) 2585.2.2 Giant Magnetoresistance (GMR) Effect 2595.2.3 Colossal Magnetoresistance (CMR) in Perovskite Oxomanganates 2615.2.4 Tunnelling Magnetoresistance (TMR) and Magnetic Tunnel Junctions (MTJ) 2635.2.5 Powder, Intrinsic and Extrinsic MR 2635.3 Half-Metallicity 2645.3.1 Half-Metallicity in Heusler Alloys 2645.3.2 Half-Metallic Ferro/Ferrimagnets, Antiferromagnets 2655.4 Oxides Exhibiting Half-Metallicity 2665.4.1 CrO2 2665.4.2 Fe3O4 and Other Spinel Oxides 2685.4.3 Perovskite Oxomanganates 2705.4.4 Double Perovskites 2725.5 Magnetoresistance and Half-Metallicity of Double Perovskites 2735.5.1 Double Perovskite Structure 2735.5.2 Ordering and Anti-Site (AS) Disorder in Double Perovskites 2765.5.3 Electronic Structure and Magnetic Properties of Double Perovskites 2815.5.4 Magnetoresistance and Half-Metallicity in Double Perovskites 2845.5.5 High Curie Temperature (TC) Double Perovskites and Room Temperature MR 2855.6 Spintronics – The Emerging Magneto-Electronics 2865.7 Summary 288Acknowledgements 289References 289Index 295