FUNCTIONALIZATION OF SEMICONDUCTOR SURFACES -- CONTENTS -- Preface -- Contributors -- 1. Introduction -- 1.1 Motivation for a Book on Functionalization of Semiconductor Surfaces -- 1.2 Surface Science as the Foundation of the Functionalization of Semiconductor Surfaces -- 1.2.1 Brief Description of the Development of Surface Science -- 1.2.2 Importance of Surface Science -- 1.2.3 Chemistry at the Interface of Two Phases -- 1.2.4 Surface Science at the Nanoscale -- 1.2.5 Surface Chemistry in the Functionalization of Semiconductor Surfaces -- 1.3 Organization of this Book -- References -- 2. Surface Analytical Techniques -- 2.1 Introduction -- 2.2 Surface Structure -- 2.2.1 Low-Energy Electron Diffraction -- 2.2.2 Ion Scattering Methods -- 2.2.3 Scanning Tunneling Microscopy and Atomic Force Microscopy -- 2.3 Surface Composition, Electronic Structure, and Vibrational Properties -- 2.3.1 Auger Electron Spectroscopy -- 2.3.2 Photoelectron Spectroscopy -- 2.3.3 Inverse Photoemission Spectroscopy -- 2.3.4 Vibrational Spectroscopy -- 2.3.4.1 Infrared Spectroscopy -- 2.3.4.2 High-Resolution Electron Energy Loss Spectroscopy -- 2.3.5 Synchrotron-Based Methods -- 2.3.5.1 Near-Edge X-Ray Absorption Fine Structure Spectroscopy -- 2.3.5.2 Energy Scanned PES -- 2.3.5.3 Glancing Incidence X-Ray Diffraction -- 2.4 Kinetic and Energetic Probes -- 2.4.1 Thermal Programmed Desorption -- 2.4.2 Molecular Beam Sources -- 2.5 Conclusions -- References -- 3. Structures of Semiconductor Surfaces and Origins of Surface Reactivity with Organic Molecules -- 3.1 Introduction -- 3.2 Geometry, Electronic Structure, and Reactivity of Clean Semiconductor Surfaces -- 3.2.1 Si(100)-(2 X 1), Ge(100)-(2 X 1), and Diamond(100)-(2 X 1) Surfaces -- 3.2.2 Si(111)-(7 X 7) Surface -- 3.3 Geometry and Electronic Structure of H-Terminated Semiconductor Surfaces.

3.3.1 Preparation and Structure of H-Terminated Semiconductor Surfaces Under UHV -- 3.3.2 Preparation and Structure of H-Terminated Semiconductor Surfaces in Solution -- 3.3.3 Preparation and Structure of H-Terminated Semiconductor Surfaces Through Hydrogen Plasma Treatment -- 3.3.4 Reactivity of H-Terminated Semiconductor Surface Prepared Under UHV -- 3.3.5 Preparation and Structure of Partially H-Terminated Semiconductor Surfaces -- 3.3.6 Reactivity of Partially H-Terminated Semiconductor Surfaces Under Vacuum -- 3.4 Geometry and Electronic Structure of Halogen-Terminated Semiconductor Surfaces -- 3.4.1 Preparation of Halogen-Terminated Semiconductor Surfaces Under UHV -- 3.4.2 Preparation of Halogen-Terminated Semiconductor Surfaces from H-Terminated Semiconductor Surfaces -- 3.5 Reactivity of Hydrogen- or Halogen-Terminated Semiconductor Surfaces in Solution -- 3.5.1 Reactivity of Si and Ge Surfaces in Solution -- 3.5.2 Reactivity of Diamond Surfaces in Solution -- 3.6 Summary -- Acknowledgments -- References -- 4. Pericyclic Reactions of Organic Molecules at Semiconductor Surfaces -- 4.1 Introduction -- 4.2 [2 + 2] Cycloaddition of Alkenes and Alkynes -- 4.2.1 Ethylene -- 4.2.2 Acetylene -- 4.2.3 Cis- and Trans-2-Butene -- 4.2.4 Cyclopentene -- 4.2.5 [2 + 2]-Like Cycloaddition on Si(111)-(7 X 7) -- 4.3 [4 + 2] Cycloaddition of Dienes -- 4.3.1 1,3-Butadiene and 2,3-Dimethyl-1,3-Butadiene -- 4.3.2 1,3-Cyclohexadiene -- 4.3.3 Cyclopentadiene -- 4.3.4 [4 + 2]-Like Cycloaddition on Si(111)-(7 X 7) -- 4.4 Cycloaddition of Unsaturated Organic Molecules Containing One or More Heteroatom -- 4.4.1 C=O-Containing Molecules -- 4.4.2 Nitriles -- 4.4.3 Isocyanates and Isothiocyanates -- 4.5 Summary -- Acknowledgment -- References -- 5. Chemical Binding of Five-Membered and Six-Membered Aromatic Molecules -- 5.1 Introduction.

5.2 Five-Membered Aromatic Molecules Containing One Heteroatom -- 5.2.1 Thiophene, Furan, and Pyrrole on Si(111)-(7 X 7) -- 5.2.2 Thiophene, Furan, and Pyrrole on Si(100) and Ge(100) -- 5.3 Five-Membered Aromatic Molecules Containing Two Different Heteroatoms -- 5.4 Benzene -- 5.4.1 Different Binding Configurations on (100) Face of Silicon and Germanium -- 5.4.2 Di-Sigma Binding on Si(111)-(7 X 7) -- 5.5 Six-Membered Heteroatom Aromatic Molecules -- 5.6 Six-Membered Aromatic Molecules Containing Two Heteroatoms -- 5.7 Electronic and Structural Factors of the Semiconductor Surfaces for the Selection of Reaction Channels of Five-Membered and Six-Membered Aromatic Rings -- References -- 6. Influence of Functional Groups in Substituted Aromatic Molecules on the Selection of Reaction Channel in Semiconductor Surface Functionalization -- 6.1 Introduction -- 6.1.1 Scope of this Chapter -- 6.1.2 Structure of Most Common Elemental Semiconductor Surfaces: Comparison of Silicon with Germanium and Carbon -- 6.1.3 Brief Overview of the Types of Chemical Reactions Relevant for Aromatic Surface Modification of Clean Semiconductor Surfaces -- 6.2 Multifunctional Aromatic Reactions on Clean Silicon Surfaces -- 6.2.1 Homoaromatic Compounds Without Additional Functional Groups -- 6.2.2 Functionalized Aromatics -- 6.2.2.1 Dissociative Addition -- 6.2.2.2 Cycloaddition -- 6.2.3 Heteroaromatics: Aromaticity as a Driving Force in Surface Processes -- 6.2.4 Chemistry of Aromatic Compounds on Partially Hydrogen-Covered Silicon Surfaces -- 6.2.5 Delivery of Aromatic Groups onto a Fully Hydrogen Covered Silicon Surface -- 6.2.5.1 Hydrosilylation -- 6.2.5.2 Cyclocondensation -- 6.2.6 Delivery of Aromatic Compounds onto Protected Silicon Substrates -- 6.3 Summary -- Acknowledgments -- References -- 7. Covalent Binding of Polycyclic Aromatic Hydrocarbon Systems.

7.1 Introduction -- 7.2 PAHs on Si(100)-(2 X 1) -- 7.2.1 Naphthalene and Anthracene on Si(100)-(2 X 1) -- 7.2.2 Tetracene on Si(100)-(2 X 1) -- 7.2.3 Pentacene on Si(100)-(2 X 1) -- 7.2.4 Perylene on Si(100)-(2 X 1) -- 7.2.5 Coronene on Si(100)-(2 X 1) -- 7.2.6 Dibenzo[a, j ]coronene on Si(100)-(2 X 1) -- 7.2.7 Acenaphthylene on Si(100)-(2 X 1) -- 7.3 PAHs on Si(111)-(7 X 7) -- 7.3.1 Naphthalene on Si(111)-(7 X 7) -- 7.3.2 Tetracene on Si(111)-(7 X 7) -- 7.3.3 Pentacene on Si(111)-(7 X 7) -- 7.4 Summary -- References -- 8. Dative Bonding of Organic Molecules -- 8.1 Introduction -- 8.1.1 What is Dative Bonding? -- 8.1.2 Periodic Trends in Dative Bond Strength -- 8.1.3 Examples of Dative Bonding: Ammonia and Phosphine on Si(100) and Ge(100) -- 8.2 Dative Bonding of Lewis Bases (Nucleophilic) -- 8.2.1 Aliphatic Amines -- 8.2.1.1 Primary, Secondary, and Tertiary Amines on Si(100) and Ge(100) -- 8.2.1.2 Cyclic Aliphatic Amines on Si(100) and Ge(100) -- 8.2.1.3 Ethylenediamine on Ge(100) -- 8.2.2 Aromatic Amines -- 8.2.2.1 Aniline on Si(100) and Ge(100) -- 8.2.2.2 Five-Membered Heteroaromatic Amines: Pyrrole on Si(100) and Ge(100) -- 8.2.2.3 Six-Membered Heteroaromatic Amines -- 8.2.3 O-Containing Molecules -- 8.2.3.1 Alcohols on Si(100) and Ge(100) -- 8.2.3.2 Ketones on Si(100) and Ge(100) -- 8.2.3.3 Carboxyl Acids on Si(100) and Ge(100) -- 8.2.4 S-Containing Molecules -- 8.2.4.1 Thiophene on Si(100) and Ge(100) -- 8.3 Dative Bonding of Lewis Acids (Electrophilic) -- 8.4 Summary -- References -- 9. Ab Initio Molecular Dynamics Studies of Conjugated Dienes on Semiconductor Surfaces -- 9.1 Introduction -- 9.2 Computational Methods -- 9.2.1 Density Functional Theory -- 9.2.2 Ab Initio Molecular Dynamics -- 9.2.3 Plane Wave Bases and Surface Boundary Conditions -- 9.2.4 Electron Localization Methods -- 9.3 Reactions on the Si(100)-(2 X 1) Surface.

9.3.1 Attachment of 1,3-Butadiene to the Si(100)-(2 X 1) Surface -- 9.3.2 Attachment of 1,3-Cyclohexadiene to the Si(100)-(2 X 1) Surface -- 9.4 Reactions on the SiC(100)-(3 X 2) Surface -- 9.5 Reactions on the SiC(100)-(2 X 2) Surface -- 9.6 Calculation of STM Images: Failure of Perturbative Techniques -- References -- 10. Formation of Organic Nanostructures on Semiconductor Surfaces -- 10.1 Introduction -- 10.2 Experimental -- 10.3 Results and Discussion -- 10.3.1 Individual 1D Nanostructures on Si(100)-H: STM Study -- 10.3.1.1 Styrene and Its Derivatives on Si(100)-(2 X 1)-H -- 10.3.1.2 Long-Chain Alkenes on Si(100)-(2 X 1)-H -- 10.3.1.3 Cross-Row Nanostructure -- 10.3.1.4 Aldehyde and Ketone: Acetophenone - A Unique Example -- 10.3.2 Interconnected Junctions of 1D Nanostructures -- 10.3.2.1 Perpendicular Junction -- 10.3.2.2 One-Dimensional Heterojunction -- 10.3.3 UPS of 1D Nanostructures on the Surface -- 10.4 Conclusions -- Acknowledgment -- References -- 11. Formation of Organic Monolayers Through Wet Chemistry -- 11.1 Introduction, Motivation, and Scope of Chapter -- 11.1.1 Background -- 11.1.2 Formation of H-Terminated Silicon Surfaces -- 11.1.3 Stability of H-Terminated Silicon Surfaces -- 11.1.4 Approach -- 11.1.5 Outline -- 11.2 Techniques Characterizing Wet Chemically Functionalized Surfaces -- 11.2.1 X-Ray Photoelectron Spectroscopy -- 11.2.2 Infrared Absorption Spectroscopy -- 11.2.3 Secondary Ion Mass Spectrometry -- 11.2.4 Surface-Enhanced Raman Spectroscopy -- 11.2.5 Spectroscopic Ellipsometry -- 11.2.6 X-Ray Reflectivity -- 11.2.7 Contact Angle, Wettability -- 11.2.8 Photoluminescence -- 11.2.9 Electrical Measurements -- 11.2.10 Imaging Techniques -- 11.2.11 Electron and Atom Diffraction Methods -- 11.3 Hydrosilylation of H-Terminated Surfaces -- 11.3.1 Catalyst-Aided Reactions -- 11.3.2 Photochemically Induced Reactions.

11.3.3 Thermally Activated Reactions.