Functional oxides

Functional oxides have a wide variety of applications in the electronic industry. The discovery of new metal oxides with interesting and useful properties continues to drive much research in chemistry, physics, and materials science.

In Functional Oxides five topical areas have been selected to illustrate the importance of metal oxides in modern materials chemistry:

Noncentrosymmetric Inorganic Oxide Materials Geometrically Frustrated Magnetic Materials Lithium Ion Conduction in Oxides Thermoelectric Oxides Transition Metal Oxides - Magnetoresistance and Half-Metallicity

The contents highlight structural chemistry, magnetic and electronic properties, ionic conduction and other emerging areas of importance, such as thermoelectricity and spintronics.

Functional Oxides covers these complex concepts in a clear and accessible manner providing an excellent introduction to this broad subject area.

Author Notes

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.

P. Shiv HalasyamaniJohn E. GreedanEdmund CussenSylvie Hébert and Antoine MaignanTapas Kumar Mandal and Martha Greenblatt

Inorganic Materials Series Preface	p. ix
Preface	p. xi
List of Contributors	p. xiii
1 Noncentrosymmetric Inorganic Oxide Materials: Synthetic Strategies and Characterisation Techniques	p. 1
1.1 Introduction	p. 1
1.2 Strategies toward Synthesising Noncentrosymmetric Inorganic Materials	p. 3
1.3 Electronic Distortions	p. 4
1.3.1 Metal Oxyfluoride Systems	p. 8
1.3.2 Salt-Inclusion Solids	p. 9
1.3.3 Borates	p. 11
1.3.4 Noncentrosymmetric Coordination Networks	p. 12
1.4 Properties Associated with Noncentrosymmetric Materials	p. 16
1.4.1 Second-Harmonic Generation	p. 18
1.4.2 Piezoelectricity	p. 21
1.4.3 Pyroelectricity	p. 25
1.4.4 Ferroelectricity	p. 27
1.5 Outlook - Multifunctional Materials	p. 30
1.5.1 Perovskites	p. 31
1.5.2 Hexagonal Manganites	p. 32
1.5.3 Metal Halide and Oxy-Halide Systems	p. 32
1.6 Concluding Thoughts	p. 33
1.6.1 State of the Field	p. 33
Acknowledgements	p. 34
References	p. 34
2 Geometrically Frustrated Magnetic Materials	p. 41
2.1 Introduction	p. 41
2.2 Geometric Frustration	p. 42
2.2.1 Definition and Criteria: Subversion of the Third Law	p. 42
2.2.2 Magnetism Short Course	p. 43
2.2.3 Frustrated Lattices - The Big Four	p. 46
2.2.4 Ground States of Frustrated Systems: Consequences of Macroscopic Degeneracy	p. 46
2.3 Real Materials	p. 52
2.3.1 The Triangular Planar (TP) Lattice	p. 52
2.3.2 The Kagomé Lattice	p. 57
2.3.3 The Face-Centred Cubic Lattice	p. 72
2.3.4 The Pyrochlores and Spinels	p. 76
2.3.5 Other Frustrated Lattices	p. 105
2.4 Concluding Remarks	p. 108
References	p. 109
3 Lithium Ion Conduction in Oxides	p. 119
3.1 Introduction	p. 119
3.2 Sodium and Lithium ß-Alumina	p. 126
3.3 Akali Metal Sulfates and the Effect of Anion Disorder on Conductivity	p. 132
3.4 LISICON and Related Phases	p. 145
3.5 Lithium Conduction in NASICON-Related Phases	p. 155
3.6 Doped Analogues of LiZr 2 (PO 4 ) 3	p. 164
3.7 Lithium Conduction in the Perovskite Structure	p. 175
3.7.1 The Structures of Li 3x La 2/3-x TiO 3	p. 181
3.7.2 Doping Studies of Lithium Perovskites	p. 185
3.8 Lithium-Containing Garnets	p. 187
References	p. 197
4 Thermoelectric Oxides	p. 203
4.1 Introduction	p. 203
4.2 How to Optimise Thermoelectric Generators (TEG)	p. 204
4.2.1 Principle of a TEG	p. 204
4.2.2 The Figure of Merit	p. 207
4.2.3 Beyond the Classical Approach	p. 210
4.3 Thermoelectric Oxides	p. 213
4.3.1 Semiconducting Oxides and the Heikes Formula	p. 215
4.3.2 Na x CoO 2 and the Misfit Cobaltate Family	p. 221
4.3.3 Degenerate Semiconductors	p. 240
4.3.4 All-Oxide Modules	p. 249
4.4 Conclusion	p. 251
Acknowledgements	p. 252
References	p. 252
5 Transition Metal Oxides: Magnetoresistance and Half-Metallicity	p. 257
5.1 Introduction	p. 257
5.2 Magnetoresistance: Concepts and Development	p. 258
5.2.1 Phenomenon of Magnetoresistance: Metallic Multilayers and Anisotropic Magnetoresistance (AMR)	p. 258
5.2.2 Giant Magnetoresistance (GMR) Effect	p. 259
5.2.3 Colossal Magnetoresistance (CMR) in Perovskite Oxomanganates	p. 261
5.2.4 Tunnelling Magnetoresistance (TMR) and Magnetic Tunnel Junctions (MTJ)	p. 263
5.2.5 Powder, Intrinsic and Extrinsic MR	p. 263
5.3 Half-Metallicity	p. 264
5.3.1 Half-Metallicity in Heusler Alloys	p. 264
5.3.2 Half-Metallic Ferro/Ferrimagnets, Antiferromagnets	p. 265
5.4 Oxides Exhibiting Half-Metallicity	p. 266
5.4.1 CrO 2	p. 266
5.4.2 Fe 3 O 4 and Other Spinel Oxides	p. 268
5.4.3 Perovskite Oxomanganates	p. 270
5.4.4 Double Perovskites	p. 272
5.5 Magnetoresistance and Half-Metallicity of Double Perovskites	p. 273
5.5.1 Double Perovskite Structure	p. 273
5.5.2 Ordering and Anti-Site (AS) Disorder in Double Perovskites	p. 276
5.5.3 Electronic Structure and Magnetic Properties of Double Perovskites	p. 281
5.5.4 Magnetoresistance and Half-Metallicity in Double Perovskites	p. 284
5.5.5 High Curie Temperature (T C ) Double Perovskites and Room Temperature MR	p. 285
5.6 Spintronics - The Emerging Magneto-Electronics	p. 286
5.7 Summary	p. 288
Acknowledgements	p. 289
References	p. 289
Index	p. 295

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