Treatise on Solid State Chemistry

of Volume 6A.- 1 The Structure and Thermodynamics of Clean Surfaces—Principles.- 1. Introduction.- 2. Thermodynamics of Surfaces.- 2.1. Estimation of Specific Surface Free Energies.- 2.2. The Effect of Surface Tension on Growth and Surface Reactions.- 2.3. Surface Tension of Multicomponent Systems.- 2.4. The Surface Composition of an Ideal Binary Solution.- 2.5. Thermodynamic Properties of Curved Surfaces.- 3. The Structure of Surfaces.- 4. The Atomic Structure of Clean Surfaces.- 4.1. Nomenclature.- 4.2. Unreconstructed Surfaces That Exhibit Contraction (Expansion) Perpendicular to the Surface Plane or Changes in Chemical Composition.- 4.3. Surface Reconstruction.- 4.4. Stepped High-Miller-Index Surfaces.- 4.5. Detection of Surface Disorder on an Atomic Scale.- 5. The Electronic Structure of Surfaces.- 5.1. The Theory of Electron Surface States.- 5.2. Changes of Work Function.- 5.3. The Studies of Electronic Structure at Surfaces by Emission and Recombination Involving Inner Shell Electrons.- Acknowledgment.- References.- 2 Surface Structure—Experimental Methods.- 1. Introduction.- 1.1. Scope and Organization.- 1.2. Importance of Surface Purity and Surface Order.- 1.3. Experimental Methods.- 2. Chemical Structure.- 2.1. Core-Level Spectroscopies.- 2.2. Ion Scattering Spectroscopy.- 2.3. Secondary Ion Emission and Desorption Methods.- 3. Geometric Structure.- 3.1. Field Ion Microscopy.- 3.2. Reflection Electron Diffraction.- 3.3. Ion and Atom Scattering.- 3.4. High-Resolution Electron Spectroscopy.- 4. Surface Electronic Structure.- 4.1. Characterization of Electronic Structure.- 4.2. Kinds of Experimental Methods.- 4.3. Electron Spectroscopies for Filled States.- 4.4. Electron Spectroscopies for Unfilled States.- 4.5. Basic Characteristics of Surface Electron Spectroscopies.- 4.6. Optical Methods of Studying Surface Electronic Structures.- 4.7. Methods Based on the Semiconductor Space-Charge Layer.- 4.8. Inelastic LEED and Surface Plasmon Dispersion.- Acknowledgments.- References.- 3 Evaporation from Solids.- 1. Introduction.- 2. Principles.- 2.1. Introduction to Kinetic Principles.- 2.2. Vaporization, Condensation, and Thermal Accommodation Coefficients.- 2.3. Introduction to Thermodynamic Principles.- 2.4. Free Evaporation.- 2.5. Systems with More than One Vapor Species.- 3. Experimental Methods.- 3.1. Measurements of Vaporization Rates Far from Equilibrium.- 3.2. Measurements of Vaporization Rates Near Equilibrium.- 3.3. Measurements of Vaporization Coefficients.- 3.4. Supplemental Experiments.- 4. Evaporation Mechanisms of Single Crystals.- 4.1. The Terrace-Ledge-Kink Model.- 4.2. Elements and Isotropic Molecular Solids.- 4.3. Nondissociating Ionic Solids.- 4.4. Dissociating Solids.- 4.5. Associating Vapors.- 5. Sources of Information on Evaporation Rates.- 5.1. Compilations of Vaporization Coefficients for Solids.- 5.2. Sources of Vapor Pressure Data for Solids.- Acknowledgments.- References.- 4 Molecular Beam Deposition of Solids on Surfaces: Ultrathin Films.- 1. Introduction.- 2. Kinetic Impediments for Condensation.- 2.1. Atom—Surface Interaction.- 2.2. Molecule—Surface Interaction.- 3. Nucleation of Solids and Liquids on Surfaces: Theory.- 3.1. Adsorption and Nucleation: Classification of Interfacial Interactions into Four Types.- 3.2. Type I Deposition: Weak Interaction with the Substrate.- 3.3. Type II Deposition: Medium Strong Interaction with the Substrate and Small Lattice Mismatch.- 3.4. Type III Deposition: Strong Interaction, Large Misfit; and Type IV, Reactive Deposition.- 3.5. Computer Simulation of Vapor Deposition.- 4. Experimental Techniques.- 4.1. Molecular Beam Methods.- 4.2. In Situ Transmission Electron Microscopy.- 4.3. Scanning High-Energy Electron Diffraction (SHEED).- 4.4. Multiple Ion Reflection.- 4.5. Field Ion Microscopy (FIM) and Field Emission Microscopy (FEM).- 5. Deposition of Semiconductors.- 5.1. Silicon.- 5.2. Germanium.- 5.3. Gallium Arsenide and Gallium Phosphide.- 5.4. II–VI Compound Semiconductors.- 6. Deposition of Metals.- 6.1. Deposition onto Ionic Substrates and Layered Compounds.- 6.2. Metals on Nonrefractory Metals.- 6.3. Refractory Metal Substrates.- 6.4. Metals on Semiconductors.- 7. Deposition of Thin Films of Noble Gases and Saturated Molecules.- 7.1. Structure of Adsorbed Layers.- 7.2. Kinetics of Nucleation and Growth.- 8. Summary.- List of Symbols.- Acknowledgments.- References.- 5 Adsorption of Gases on Solids.- 1. Introduction.- 1.1. Objectives and Approach.- 1.2. Nature and Development of the Subject.- 1.3. Microscopic Adsorption Properties.- 2. Phenomenological Models and Atomistic Concepts.- 2.1. Nature of Adsorbed Layers.- 2.2. Atomic Composition of Surface Layers.- 2.3. Surface Coverage Measurement.- 2.4. Energetics and Kinetics of Adsorption.- 2.5. Change in Work Function.- 2.6. Atomic Geometry of Surface Layers.- 2.7. Collective Interactions in Adsorption.- 2.8. Vibrational Properties of Adsorbed Layers.- 3. Electronic Properties of Adsorbed Layers.- 3.1. Theoretical Approaches to Chemisorption.- 3.2. Experimental Approaches to Chemisorption.- 4. Some Prototype Adsorption Systems.- 4.1. Adsorption of Diatomic Gases on Tungsten.- 4.2. Adsorption of Oxygen, Sulfur, Selenium, and Tellurium on Nickel.- 5. Summary and Conclusions.- 5.1. Status of Present Work.- 5.2. Directions for Future Study.- Acknowledgments.- References.