The Defect Chemistry of Metal Oxides

1. Introduction Reference 2. A Few Useful Crystal Structures Introduction Close-Packed Structures Structures for Eight-Coordinate Cations Structures for Ternary Compounds Conclusion References Problems 3. Lattice Defects and the Law of Mass Action Introduction Lattice Defects as Part of the Equilibrium State The Law of Mass Action Another View of Mass Action Lattice Disorder in Elemental Solids Summary References 4. Intrinsic Ionic Disorder Lattice Defects and Reference States Conservation Rules Defect Notation Major Types of Intrinsic Ionic Disorder General Comments on Intrinsic Ionic Disorder References Problems 5. Extrinsic Ionic Disorder Introduction The AgCl-CdCl[2 System The CaF[2-CaO System The TiO[2-Nb[2O[5 System Summary of Important Points Schematic Representation of Defect Concetrations Summary of Extrinsic Ionic Disorder References Problems 6. Defect Complexes and Associates Introduction Complexes Containing an Impurity Center and an Ionic Defect Intrinsic Ionic Defect Associates The Effect of Impurities on the Concentrations of Defect Complexes and Associates References 7. Ionic Transport Introduction Basic Concepts of Diffusion Ionic Conduction in Crystalline Solids Intrinsic and Extrinsic Ionic Conduction Fast Ion Conductors References 8. Intrinsic Electronic Disorder Introduction The Development of Energy Bonds The Mass-Action Approach The Fermi Function Holes, Waves, and Effective Masses Electronic Conductivity Hopping Mechanisms The Band Structure of Compounds Chemistry and the Band Gap Summary References 9. Extrinsic Electronic Disorder Introduction Interactions with the Gaseous Ambient The Choice of Compensating Defect The Chemical Consequences of Electronic Compensation The Interactions of Impurity Centers with Electrons and Holes The Situation for Compounds Summary References 10. Intrinsic Nonstoichiometry Introduction Nonstoichiometry in Pure Crystalline Compounds Nonstoichiometry and Equilibrium Defect Concentrations The Hypothetical Compund MX with Schottky Disorder Summary of the Kroeger-Vink Diagram for MX Conclusion of the Discussion of MX A More Complex Kroeger-Vink Diagram Summary of the Kroeger-Vink Diagrams for Intrinsic Nonstoichiometry Enthalpy Relationships Conclusion Reference Problems 11. Extrinsic Nonstoichiometry Introduction A Simple Example: Donor-Doped MX Enthalpy Relationships A More Complex Example: Acceptor-Doped M[2O[3 General Considerations Nonstoichiometric Reactions in the Impurity-Controlled Region Problems 12. Titanium Dioxide Introduction The Amount of Nonstoichiometry The Equilibrium Electrical Conductivity of Undoped TiO[2 The Seebeck Coefficient of Undoped TiO[2 Ionic Conduction in TiO[2 The Effect of Dopants on TiO[2 General Comments on the Defect Chemistry of TiO[2 References Problems 13. Cobalt Oxide and Nickel Oxide Introduction Cobaltous Oxide, CoO Nickelous Oxide, NiO Summary References 14. Barium Titanate Introduction General Expectations The Equilibrium Conductivity of Undoped BaTiO[3 Insulating Properties of BaTiO[3 Acceptor-Doped BaTiO[3 Ionic Conduction in BaTiO[3 Donor-Doped BaTiO[3 Trivalent Dopants in BaTiO[3 Summary References 15. Order versus Disorder Block Structures Summary References Index