Photoelectron Spectroscopy

Transcription

1 Stefan Hüfner Photoelectron Spectroscopy Principles and Applications Third Revised and Enlarged Edition With 461 Figures and 28 Tables JSJ Springer

2 Introduction and Basic Principles Historical Development The Electron Mean Free Path Photoelectron Spectroscopy and Inverse Photoelectron Spectroscopy Experimental Aspects Very High Resolution 27 l.g The Theory of Photoemission Gore-Level Photoemission Valence-State Photoemission Three-Step and One-Step Considerations Dcviations from the Simple Theory of Photoemission 51 References Core Levels and Final States Core-Levcl Binding Energies in Atoms and Moleculcs The Equivalent-Core Approximation Chemical Shifts Corc-Lcvel Binding Energies in Solids The Born Haber Cycle in Insulators Theory of Binding Energies Determination of Binding Energies and Chemical Shifts from Thermodynamic Data Core Polarization Final-State Multiplets in Rare-Earth Valence Bands Vibrational Side Bands Gore Levels of Adsorbed Molecules Quantitative Chemical Analysis from Core-Level Intensities References Charge-Excitation Final States: Satellites Copper Dihalides; 3d Transition Metal Compounds Characterization of a Satellite Analysis of Charge-Transfer Satellites 115

3 XII Non-local Screening The 6-eV Satellite in Nickel Resonance Photoemission Satellites in Other Metals The Gunnarsson-Schönhammer Theory Photoemission Signals and Narrow Bands in Metals 152 References Continuous Satellites and Plasmon Satellites: XPS Photoemission in Nearly Free Electron Systems Theory General Core-Line Shape Intrinsic Plasmons Extrinsic Electron Scattering: Plasmons and Background The Total Photoelectron Spectrum Experimental Results The Gore Line Without Plasmons Core-Level Spectra Including Plasmons Valence-Band Spectra of the Simple Metals Simple Metals: A General Comment The Background Correction 201 References Valence Orbitals in Simple Molecules and Insulating Solids UPS Spectra of Monatomic Gases Photoelectron Spectra of Diatomic Molecules Binding Energy of the H2 Molecule Hydrides Isoelectronic with Noble Gases 222 Neon (Ne) 223 Hydrogen Fluoride (HF) 223 Water (H 2 0) 223 Ammonia (NH 3 ) 224 Methane (CH 4 ) Spectra of the Alkali Halides Transition Metal Dihalides Hydrocarbons Guidelines for the Interpretation of Spectra from Free Molecules Linear Polymers Insulating Solids with Valence d Electrons The NiO Problem Mott Insulation 268

4 XIII The Metal-Insulator Transition; the Ratio of the Correlation Energy and the Bandwidth; Doping Band Structures of Transition Metal Compounds High-Temperature Superconductors Valence-Band Electronic Structure; Polycrystalline Samples Dispersion Relations in High Temperature Superconductors; Single Crystals Thc Superconducting Gap Symmetry of the Order Parameter in the High-Temperature Superconductors Core-Level Shifts The Fermi Liquid and the Luttinger Liquid Adsorbed Molecules Outline CO on Metal Surfaces 324 Rcfcrences 337 Photoemission of Valence Electrons from Metallic Solids in the One-Electron Approximation Theory of Photoemission: A Summary of the Three-Stcp Model Discussion of the Photocurrcnt Kinematics of Internal Photoemission in a Polycrystalline Sample Primary and Secondary Cones in the Photoemission from a Real Solid Angle-Integrated and Angle-Resolved Data Collection Photoemission from the Semi-infinite Crystal: The Inverse LEED Formalism Band Structure Regime XPS Regime Surface Emission One-Step Calculations Thermal Effects Dipole Selection Rules for Direct Optical Transitions 401 References 407 Band Structure and Angular-Resolved Photoelectron Spectra Free-Elcctron Final-State Model Methods Employing Calculated Band Structures Methods for the Absolute Determination of the Crystal Momentum 418

5 XIV Triangulation or Energy Coincidence Method Bragg Plane Method: Variation of External Emission Angle at Fixed Photon Frcquency (Disappearance/Appearance Angle Method Bragg Plane Method: Variation of Photon Energy at Fixed Emission Angle (Symmetry Method) The Surface Emission Method and Electron Damping The Very-Low-Energy Electron Diffraction Method The Fermi Surface Method Intensities and Their Use in Band-Structure Determinations Summary Experimental Band Structures One- and Two-Dimensional Systems Three-Dimensional Solids: Metals and Semiconductors UPS Band Structures and XPS Density of States A Comment 493 References Surface States, Surface Effects Theoretical Considerations Experimental Results on Surface States Quantum-Well States Surface Core-Level Shifts 535 References Inverse Photoelectron Spectroscopy Surface States Bulk Band Structures Adsorbed Molecules 563 References Spin-Polarized Photoelectron Spectroscopy General Description Exaniples of Spin-Polarized Photoelectron Spectroscopy Magnetic Dichroism 586 References Photoelectron Diffraction Examples Substrate Photoelectron Diffraction Adsorbate Photoelectron Diffraction Fermi Surface Scans 626 References 633

6 , XV Appendix 635 A.l Table of Binding Energies 636 A.2 Surface and Bulk Brillouin Zones of the Three Low-Index Faces of a Face-Centered Cubic (fcc) Crystal Face 642 A.3 Compilation of Work Functions 650 References 651 Index 653