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Full Description
The recent discovery of high-temperature superconductivity in copper based oxides is an event of major importance not only with respect to the physical phenomenon itself but also because it definitely shows that solid state chemistry, and especially the crystal chemistry of oxides, has a crucial place in the synthesis and understanding of new materials for future appli cations. The numerous papers published in the field of high Tc supercon ductors in the last five years demonstrate that the great complexity of these materials necessitates a close collaboration between physicists and solid state chemists. This book is based to a large extent on our experience of the crystal chemistry of copper oxides, which we have been studying in the laboratory for more than twelve years, but it also summarizes the main results which have been obtained for these compounds in the last five years relating to their spectacular superconducting properties. We have focused on the struc ture, chemical bonding and nonstoichiometry of these materials, bearing in mind that redox reactions are the key to the optimization of their supercon ducting properties, owing to the importance of the mixed valence of copper and its Jahn-Teller effect. We have also drawn on studies of extended defects by high-resolution electron microscopy and on their creation by ir radiation effects.
Contents
1. Introduction: Superconductivity in Oxides Before 1986.- 2. Phases of the Systems A-La-Ca-Cu-O and A-Y-Ca-Cu-O (A = Ca, Sr, Ba): Structural Aspects.- 2.1 Copper Chemistry in Oxides: Oxidation States and Coordination.- 2.2 The Ternary Systems La-Cu-O and A-Cu-O (A = Ca,Sr,Ba).- 2.3 The Pseudoternary Systems A-La-Cu-O (A = Ca,Sr,Ba).- 2.4 The Pseudoternary System Y-Ba-Cu-O.- 2.5 The Systems Ln-Sr-Cu-O (Ln ? La).- 3. Electron Transport Properties Connected with Oxygen Nonstoichiometry.- 3.1 Electron Transport Properties in Cuprates Related to the Perovskite: General Considerations.- 3.2 Oxides with the K2NiF4-Type Structure.- 3.3 Oxides with the Oxygen-Deficient Sr3Ti2O7-Type Structure.- 3.4 Oxides with the Oxygen-Deficient Perovskite Structure.- 4. Substitutions in La2CuO4-Type and YBa2Cu3O7-Type Superconductors.- 4.1 Substitution on the Rare-Earth Sites.- 4.2 Substitution on the Copper Sites.- 4.3 Substitutions on Other Sites.- 5. Bismuth, Thallium and Lead Superconducting Cuprates.- 5.1 Bismuth Alkaline-Earth Superconducting Cuprates.- 5.2 Thallium Alkaline-Earth Superconducting Cuprates.- 5.3 Lead Alkaline-Earth Superconducting Cuprates.- 5.4 Layered Cuprates Involving Double Fluorite-Type Layers.- 5.5 Structural Relationships.- 6. Extended Defects in Superconducting Oxides: High-Resolution Electron Microscopy.- 6.1 YBa2Cu3O7-Type Superconductors: Ordering in the Perovskite Framework.- 6.3 Layer Interconnections.- 6.4 Extra Spots in ED Patterns: An Amazing Variety.- 6.5 Domains and Boundaries.- 7. Irradiation Effects in the High-Tc Superconducting Oxides.- 7.1 Radiation Damage in Solids.- 7.2 Radiation Damage by Electrons and Fast Neutrons in Copper Oxide Superconductors.- 7.3 Phase Transformations Induced by Fast Heavy Ions in the High-Tc Copper Oxides.- 7.4Conclusions.- 8. Concluding Remarks.- 8.1 Low Dimensionality of the Structure.- 8.2 Mixed Valence of Copper and Hole Delocalization.- 8.3 The Model of Copper Disproportionation.- 8.4 Role of the Lone Pair Cations and of the Alkaline Earth Elements.- References.
