Preface xv Contributors xix 1. Introduction 1 Franklin (Feng) Tao, Yuan Zhu, and Steven L. Bernasek 1.1 Motivation for a Book on Functionalization of Semiconductor Surfaces 1 1.2 Surface Science as the Foundation of the Functionalization of Semiconductor Surfaces 2 1.2.1 Brief Description of the Development of Surface Science 2 1.2.

2 Importance of Surface Science 3 1.2.3 Chemistry at the Interface of Two Phases 4 1.2.4 Surface Science at the Nanoscale 5 1.2.5 Surface Chemistry in the Functionalization of Semiconductor Surfaces 7 1.3 Organization of this Book 7 References 9 2.

Surface Analytical Techniques 11 Ying Wei Cai and Steven L. Bernasek 2.1 Introduction 11 2.2 Surface Structure 12 2.2.1 Low-Energy Electron Diffraction 13 2.2.2 Ion Scattering Methods 14 2.

2.3 Scanning Tunneling Microscopy and Atomic Force Microscopy 15 2.3 Surface Composition, Electronic Structure, and Vibrational Properties 16 2.3.1 Auger Electron Spectroscopy 16 2.3.2 Photoelectron Spectroscopy 17 2.3.

3 Inverse Photoemission Spectroscopy 18 2.3.4 Vibrational Spectroscopy 18 2.3.4.1 Infrared Spectroscopy 19 2.3.4.

2 High-Resolution Electron Energy Loss Spectroscopy 19 2.3.5 Synchrotron-Based Methods 20 2.3.5.1 Near-Edge X-Ray Absorption Fine Structure Spectroscopy 20 2.3.5.

2 Energy Scanned PES 21 2.3.5.3 Glancing Incidence X-Ray Diffraction 21 2.4 Kinetic and Energetic Probes 21 2.4.1 Thermal Programmed Desorption 22 2.4.

2 Molecular Beam Sources 22 2.5 Conclusions 23 References 23 3. Structures of Semiconductor Surfaces and Origins of Surface Reactivity with Organic Molecules 27 Yongquan Qu and Keli Han 3.1 Introduction 27 3.2 Geometry, Electronic Structure, and Reactivity of Clean Semiconductor Surfaces 28 3.2.1 Si(100)-(2×1), Ge(100)-(2×1), and Diamond(100)-(2×1) Surfaces 29 3.2.

2 Si(111)-(7×7) Surface 33 3.3 Geometry and Electronic Structure of H-Terminated Semiconductor Surfaces 34 3.3.1 Preparation and Structure of H-Terminated Semiconductor Surfaces Under UHV 34 3.3.2 Preparation and Structure of H-Terminated Semiconductor Surfaces in Solution 35 3.3.3 Preparation and Structure of H-Terminated Semiconductor Surfaces Through Hydrogen Plasma Treatment 36 3.

3.4 Reactivity of H-Terminated Semiconductor Surface Prepared Under UHV 36 3.3.5 Preparation and Structure of Partially H-Terminated Semiconductor Surfaces 36 3.3.6 Reactivity of Partially H-Terminated Semiconductor Surfaces Under Vacuum 38 3.4 Geometry and Electronic Structure of Halogen-Terminated Semiconductor Surfaces 39 3.4.

1 Preparation of Halogen-Terminated Semiconductor Surfaces Under UHV 40 3.4.2 Preparation of Halogen-Terminated Semiconductor Surfaces from H-Terminated Semiconductor Surfaces 41 3.5 Reactivity of Hydrogen- or Halogen-Terminated Semiconductor Surfaces in Solution 41 3.5.1 Reactivity of Si and Ge Surfaces in Solution 41 3.5.2 Reactivity of Diamond Surfaces in Solution 43 3.

6 Summary 45 Acknowledgments 46 References 46 4. Pericyclic Reactions of Organic Molecules at Semiconductor Surfaces 51 Keith T. Wong and Stacey F. Bent 4.1 Introduction 51 4.2 [2+2] Cycloaddition of Alkenes and Alkynes 53 4.2.1 Ethylene 53 4.

2.2 Acetylene 57 4.2.3 Cis - and Trans -2-Butene 58 4.2.4 Cyclopentene 59 4.2.5 [2+2]-Like Cycloaddition on Si(111)-(7×7) 61 4.

3 [4+2] Cycloaddition of Dienes 62 4.3.1 1,3-Butadiene and 2,3-Dimethyl-1,3-Butadiene 63 4.3.2 1,3-Cyclohexadiene 66 4.3.3 Cyclopentadiene 67 4.3.

4 [4+2]-Like Cycloaddition on Si(111)-(7×7) 69 4.4 Cycloaddition of Unsaturated Organic Molecules Containing One or More Heteroatom 71 4.4.1 C=O-Containing Molecules 71 4.4.2 Nitriles 78 4.4.3 Isocyanates and Isothiocyanates 80 4.

5 Summary 81 Acknowledgment 83 References 83 5. Chemical Binding of Five-Membered and Six-Membered Aromatic Molecules 89 Franklin (Feng) Tao and Steven L. Bernasek 5.1 Introduction 89 5.2 Five-Membered Aromatic Molecules Containing One Heteroatom 89 5.2.1 Thiophene, Furan, and Pyrrole on Si(111)-(7×7) 90 5.2.

2 Thiophene, Furan, and Pyrrole on Si(100) and Ge(100) 92 5.3 Five-Membered Aromatic Molecules Containing Two Different Heteroatoms 95 5.4 Benzene 98 5.4.1 Different Binding Configurations on (100) Face of Silicon and Germanium 98 5.4.2 Di-Sigma Binding on Si(111)-(7×7) 99 5.5 Six-Membered Heteroatom Aromatic Molecules 100 5.

6 Six-Membered Aromatic Molecules Containing Two Heteroatoms 101 5.7 Electronic and Structural Factors of the Semiconductor Surfaces for the Selection of Reaction Channels of Five-Membered and Six-Membered Aromatic Rings 102 References 103 6. Influence of Functional Groups in Substituted Aromatic Molecules on the Selection of Reaction Channel in Semiconductor Surface Functionalization 105 Andrew V. Teplyakov 6.1 Introduction 105 6.1.1 Scope of this Chapter 105 6.1.

2 Structure of Most Common Elemental Semiconductor Surfaces: Comparison of Silicon with Germanium and Carbon 107 6.1.3 Brief Overview of the Types of Chemical Reactions Relevant for Aromatic Surface Modification of Clean Semiconductor Surfaces 111 6.2 Multifunctional Aromatic Reactions on Clean Silicon Surfaces 113 6.2.1 Homoaromatic Compounds Without Additional Functional Groups 113 6.2.2 Functionalized Aromatics 116 6.

2.2.1 Dissociative Addition 116 6.2.2.2 Cycloaddition 120 6.2.3 Heteroaromatics: Aromaticity as a Driving Force in Surface Processes 130 6.

2.4 Chemistry of Aromatic Compounds on Partially Hydrogen-Covered Silicon Surfaces 137 6.2.5 Delivery of Aromatic Groups onto a Fully Hydrogen Covered Silicon Surface 147 6.2.5.1 Hydrosilylation 147 6.2.

5.2 Cyclocondensation 148 6.2.6 Delivery of Aromatic Compounds onto Protected Silicon Substrates 150 6.3 Summary 151 Acknowledgments 152 References 152 7. Covalent Binding of Polycyclic Aromatic Hydrocarbon Systems 163 Kian Soon Yong and Guo-Qin Xu 7.1 Introduction 163 7.2 PAHs on Si(100)-(2×1) 165 7.

2.1 Naphthalene and Anthracene on Si(100)-(2×1) 165 7.2.2 Tetracene on Si(100)-(2×1) 167 7.2.3 Pentacene on Si(100)-(2×1) 169 7.2.4 Perylene on Si(100)-(2×1) 172 7.

2.5 Coronene on Si(100)-(2×1) 173 7.2.6 Dibenzo[ a , j ]coronene on Si(100)-(2×1) 174 7.2.7 Acenaphthylene on Si(100)-(2×1) 175 7.3 PAHs on Si(111)-(7×7) 176 7.3.

1 Naphthalene on Si(111)-(7×7) 176 7.3.2 Tetracene on Si(111)-(7×7) 179 7.3.3 Pentacene on Si(111)-(7×7) 184 7.4 Summary 189 References 190 8. Dative Bonding of Organic Molecules 193 Young Hwan Min, Hangil Lee, Do Hwan Kim, and Sehun Kim 8.1 Introduction 193 8.

1.1 What is Dative Bonding? 193 8.1.2 Periodic Trends in Dative Bond Strength 194 8.1.3 Examples of Dative Bonding: Ammonia and Phosphine on Si(100) and Ge(100) 197 8.2 Dative Bonding of Lewis Bases (Nucleophilic) 198 8.2.

1 Aliphatic Amines 198 8.2.1.1 Primary, Secondary, and Tertiary Amines on Si(100) and Ge(100) 198 8.2.1.2 Cyclic Aliphatic Amines on Si(100) and Ge(100) 202 8.2.

1.3 Ethylenediamine on Ge(100) 204 8.2.2 Aromatic Amines 206 8.2.2.1 Aniline on Si(100) and Ge(100) 207 8.2.

2.2 Five-Membered Heteroaromatic Amines: Pyrrole on Si(100) and Ge(100) 209 8.2.2.3 Six-Membered Heteroaromatic Amines 211 8.2.3 O-Containing Molecules 218 8.2.

3.1 Alcohols on Si(100) and Ge(100) 218 8.2.3.2 Ketones on Si(100) and Ge(100) 219 8.2.3.3 Carboxyl Acids on Si(100) and Ge(100) 220 8.

2.4 S-Containing Molecules 223 8.2.4.1 Thiophene on Si(100) and Ge(100) 223 8.3 Dative Bonding of Lewis Acids (Electrophilic) 225 8.4 Summary 226 References 229 9. Ab Initio Molecular Dynamics Studies of Conjugated Dienes on Semiconductor Surfaces 233 Mark E.

Tuckerman and Yanli Zhang 9.1 Introduction 233 9.2 Computational Methods 234 9.2.1 Density Functional Theory 235 9.2.2 Ab Initio Molecular Dynamics 237 9.2.

3 Plane Wave Bases and Surface Boundary Conditions 239 9.2.4 Electron Localization Methods 244 9.3 Reactions on the Si(100)-(2×1) Surface 247 9.3.1 Attachment of 1,3-Butadiene to the Si(100)-(2×1) Surface 249 9.3.2 Attachment of 1,3-Cyclohexadiene to the Si(100)-(2×1) Surface 257 9.

4 Reactions on the SiC(100)-(3×2) Surface 263 9.5 Reactions on the SiC(100)-(2×2) Surface 266 9.6 Calculation of STM Images: Failure of Perturbative Techniques 270 References 273 10. Formation of Organic Nanostructures on Semiconductor Surfaces 277 Md. Zakir Hossain and Maki Kawai 10.1 Introduction 277 10.2 Experimental 278 10.3 Results and Discussion 279 10.

3.1 Individual 1D Nanostructures on Si(100)-H: STM Study 279 10.3.1.1 Styrene and Its Derivatives on Si(100)-(2×1)-H 279 10.3.1.2 Long-Chain Alkenes on Si(100)-(2×1)-H 284 10.

3.1.3 Cross-Row Nanostructure 285 10.3.1.4 Aldehyde and Ketone: Acetophenone -A Unique Example 287 10.3.2 Interconnected Junctions of 1D Nanostructures 292 10.

3.2.1 Perpendicular J.