Functionalization of Semiconductor Surfaces

FRANKLIN (FENG) TAO, PHD, is Assistant Professor of Chemistry at the University of Notre Dame. His research group is actively involved in investigations of surface science, heterogeneous catalysis for efficient energy conversion, nanomaterials, and in situ studies of catalysts. Dr. Tao is the author of about 70 research articles and the recipient of the International Union of Pure and Applied Chemistry Prize for Young Chemists. STEVEN L. BERNASEK, PHD, is Professor of Chemistry at Princeton University. His research focuses on chirality in self-assembled monolayers, surface functionalization and modification, organometallic surface chemistry, and dynamics of gas-surface interactions. Dr. Bernasek is the author of more than 200 research articles. He is also the recipient of several awards, including the ACS Arthur W. Adamson Award for Distinguished Service in the Advancement of Surface Chemistry.

• Preface xvContributors xix1. Introduction 1Franklin (Feng) Tao, Yuan Zhu, and Steven L. Bernasek1.1 Motivation for a Book on Functionalization of Semiconductor Surfaces 11.2 Surface Science as the Foundation of the Functionalization of Semiconductor Surfaces 21.2.1 Brief Description of the Development of Surface Science 21.2.2 Importance of Surface Science 31.2.3 Chemistry at the Interface of Two Phases 41.2.4 Surface Science at the Nanoscale 51.2.5 Surface Chemistry in the Functionalization of Semiconductor Surfaces 71.3 Organization of this Book 7References 92. Surface Analytical Techniques 11Ying Wei Cai and Steven L. Bernasek2.1 Introduction 112.2 Surface Structure 122.2.1 Low-Energy Electron Diffraction 132.2.2 Ion Scattering Methods 142.2.3 Scanning Tunneling Microscopy and Atomic Force Microscopy 152.3 Surface Composition, Electronic Structure, and Vibrational Properties 162.3.1 Auger Electron Spectroscopy 162.3.2 Photoelectron Spectroscopy 172.3.3 Inverse Photoemission Spectroscopy 182.3.4 Vibrational Spectroscopy 182.3.4.1 Infrared Spectroscopy 192.3.4.2 High-Resolution Electron Energy Loss Spectroscopy 192.3.5 Synchrotron-Based Methods 202.3.5.1 Near-Edge X-Ray Absorption Fine Structure Spectroscopy 202.3.5.2 Energy Scanned PES 212.3.5.3 Glancing Incidence X-Ray Diffraction 212.4 Kinetic and Energetic Probes 212.4.1 Thermal Programmed Desorption 222.4.2 Molecular Beam Sources 222.5 Conclusions 23References 233. Structures of Semiconductor Surfaces and Origins of Surface Reactivity with Organic Molecules 27Yongquan Qu and Keli Han3.1 Introduction 273.2 Geometry, Electronic Structure, and Reactivity of Clean Semiconductor Surfaces 283.2.1 Si(100)-(2×1), Ge(100)-(2×1), and Diamond(100)-(2×1) Surfaces 293.2.2 Si(111)-(7×7) Surface 333.3 Geometry and Electronic Structure of H-Terminated Semiconductor Surfaces 343.3.1 Preparation and Structure of H-Terminated Semiconductor Surfaces Under UHV 343.3.2 Preparation and Structure of H-Terminated Semiconductor Surfaces in Solution 353.3.3 Preparation and Structure of H-Terminated Semiconductor Surfaces Through Hydrogen Plasma Treatment 363.3.4 Reactivity of H-Terminated Semiconductor Surface Prepared Under UHV 363.3.5 Preparation and Structure of Partially H-Terminated Semiconductor Surfaces 363.3.6 Reactivity of Partially H-Terminated Semiconductor Surfaces Under Vacuum 383.4 Geometry and Electronic Structure of Halogen-Terminated Semiconductor Surfaces 393.4.1 Preparation of Halogen-Terminated Semiconductor Surfaces Under UHV 403.4.2 Preparation of Halogen-Terminated Semiconductor Surfaces from H-Terminated Semiconductor Surfaces 413.5 Reactivity of Hydrogen- or Halogen-Terminated Semiconductor Surfaces in Solution 413.5.1 Reactivity of Si and Ge Surfaces in Solution 413.5.2 Reactivity of Diamond Surfaces in Solution 433.6 Summary 45Acknowledgments 46References 464. Pericyclic Reactions of Organic Molecules at Semiconductor Surfaces 51Keith T. Wong and Stacey F. Bent4.1 Introduction 514.2 [2+2] Cycloaddition of Alkenes and Alkynes 534.2.1 Ethylene 534.2.2 Acetylene 574.2.3 Cis- and Trans-2-Butene 584.2.4 Cyclopentene 594.2.5 [2+2]-Like Cycloaddition on Si(111)-(7×7) 614.3 [4+2] Cycloaddition of Dienes 624.3.1 1,3-Butadiene and 2,3-Dimethyl-1,3-Butadiene 634.3.2 1,3-Cyclohexadiene 664.3.3 Cyclopentadiene 674.3.4 [4+2]-Like Cycloaddition on Si(111)-(7×7) 694.4 Cycloaddition of Unsaturated Organic Molecules Containing One or More Heteroatom 714.4.1 C=O-Containing Molecules 714.4.2 Nitriles 784.4.3 Isocyanates and Isothiocyanates 804.5 Summary 81Acknowledgment 83References 835. Chemical Binding of Five-Membered and Six-Membered Aromatic Molecules 89Franklin (Feng) Tao and Steven L. Bernasek5.1 Introduction 895.2 Five-Membered Aromatic Molecules Containing One Heteroatom 895.2.1 Thiophene, Furan, and Pyrrole on Si(111)-(7×7) 905.2.2 Thiophene, Furan, and Pyrrole on Si(100) and Ge(100) 925.3 Five-Membered Aromatic Molecules Containing Two Different Heteroatoms 955.4 Benzene 985.4.1 Different Binding Configurations on (100) Face of Silicon and Germanium 985.4.2 Di-Sigma Binding on Si(111)-(7×7) 995.5 Six-Membered Heteroatom Aromatic Molecules 1005.6 Six-Membered Aromatic Molecules Containing Two Heteroatoms 1015.7 Electronic and Structural Factors of the Semiconductor Surfaces for the Selection of Reaction Channels of Five-Membered and Six-Membered Aromatic Rings 102References 1036. Influence of Functional Groups in Substituted Aromatic Molecules on the Selection of Reaction Channel in Semiconductor Surface Functionalization 105Andrew V. Teplyakov6.1 Introduction 1056.1.1 Scope of this Chapter 1056.1.2 Structure of Most Common Elemental Semiconductor Surfaces: Comparison of Silicon with Germanium and Carbon 1076.1.3 Brief Overview of the Types of Chemical Reactions Relevant for Aromatic Surface Modification of Clean Semiconductor Surfaces 1116.2 Multifunctional Aromatic Reactions on Clean Silicon Surfaces 1136.2.1 Homoaromatic Compounds Without Additional Functional Groups 1136.2.2 Functionalized Aromatics 1166.2.2.1 Dissociative Addition 1166.2.2.2 Cycloaddition 1206.2.3 Heteroaromatics: Aromaticity as a Driving Force in Surface Processes 1306.2.4 Chemistry of Aromatic Compounds on Partially Hydrogen-Covered Silicon Surfaces 1376.2.5 Delivery of Aromatic Groups onto a Fully Hydrogen Covered Silicon Surface 1476.2.5.1 Hydrosilylation 1476.2.5.2 Cyclocondensation 1486.2.6 Delivery of Aromatic Compounds onto Protected Silicon Substrates 1506.3 Summary 151Acknowledgments 152References 1527. Covalent Binding of Polycyclic Aromatic Hydrocarbon Systems 163Kian Soon Yong and Guo-Qin Xu7.1 Introduction 1637.2 PAHs on Si(100)-(2×1) 1657.2.1 Naphthalene and Anthracene on Si(100)-(2×1) 1657.2.2 Tetracene on Si(100)-(2×1) 1677.2.3 Pentacene on Si(100)-(2×1) 1697.2.4 Perylene on Si(100)-(2×1) 1727.2.5 Coronene on Si(100)-(2×1) 1737.2.6 Dibenzo[a, j ]coronene on Si(100)-(2×1) 1747.2.7 Acenaphthylene on Si(100)-(2×1) 1757.3 PAHs on Si(111)-(7×7) 1767.3.1 Naphthalene on Si(111)-(7×7) 1767.3.2 Tetracene on Si(111)-(7×7) 1797.3.3 Pentacene on Si(111)-(7×7) 1847.4 Summary 189References 1908. Dative Bonding of Organic Molecules 193Young Hwan Min, Hangil Lee, Do Hwan Kim, and Sehun Kim8.1 Introduction 1938.1.1 What is Dative Bonding? 1938.1.2 Periodic Trends in Dative Bond Strength 1948.1.3 Examples of Dative Bonding: Ammonia and Phosphine on Si(100) and Ge(100) 1978.2 Dative Bonding of Lewis Bases (Nucleophilic) 1988.2.1 Aliphatic Amines 1988.2.1.1 Primary, Secondary, and Tertiary Amines on Si(100) and Ge(100) 1988.2.1.2 Cyclic Aliphatic Amines on Si(100) and Ge(100) 2028.2.1.3 Ethylenediamine on Ge(100) 2048.2.2 Aromatic Amines 2068.2.2.1 Aniline on Si(100) and Ge(100) 2078.2.2.2 Five-Membered Heteroaromatic Amines: Pyrrole on Si(100) and Ge(100) 2098.2.2.3 Six-Membered Heteroaromatic Amines 2118.2.3 O-Containing Molecules 2188.2.3.1 Alcohols on Si(100) and Ge(100) 2188.2.3.2 Ketones on Si(100) and Ge(100) 2198.2.3.3 Carboxyl Acids on Si(100) and Ge(100) 2208.2.4 S-Containing Molecules 2238.2.4.1 Thiophene on Si(100) and Ge(100) 2238.3 Dative Bonding of Lewis Acids (Electrophilic) 2258.4 Summary 226References 2299. Ab Initio Molecular Dynamics Studies of Conjugated Dienes on Semiconductor Surfaces 233Mark E. Tuckerman and Yanli Zhang9.1 Introduction 2339.2 Computational Methods 2349.2.1 Density Functional Theory 2359.2.2 Ab Initio Molecular Dynamics 2379.2.3 Plane Wave Bases and Surface Boundary Conditions 2399.2.4 Electron Localization Methods 2449.3 Reactions on the Si(100)-(2×1) Surface 2479.3.1 Attachment of 1,3-Butadiene to the Si(100)-(2×1) Surface 2499.3.2 Attachment of 1,3-Cyclohexadiene to the Si(100)-(2×1) Surface 2579.4 Reactions on the SiC(100)-(3×2) Surface 2639.5 Reactions on the SiC(100)-(2×2) Surface 2669.6 Calculation of STM Images: Failure of Perturbative Techniques 270References 27310. Formation of Organic Nanostructures on Semiconductor Surfaces 277Md. Zakir Hossain and Maki Kawai10.1 Introduction 27710.2 Experimental 27810.3 Results and Discussion 27910.3.1 Individual 1D Nanostructures on Si(100)–H: STM Study 27910.3.1.1 Styrene and Its Derivatives on Si(100)-(2×1)–H 27910.3.1.2 Long-Chain Alkenes on Si(100)-(2×1)–H 28410.3.1.3 Cross-Row Nanostructure 28510.3.1.4 Aldehyde and Ketone: Acetophenone –A Unique Example 28710.3.2 Interconnected Junctions of 1D Nanostructures 29210.3.2.1 Perpendicular Junction 29210.3.2.2 One-Dimensional Heterojunction 29510.3.3 UPS of 1D Nanostructures on the Surface 29610.4 Conclusions 298Acknowledgment 299References 29911. Formation of Organic Monolayers Through Wet Chemistry 301Damien Aureau and Yves J. Chabal11.1 Introduction, Motivation, and Scope of Chapter 30111.1.1 Background 30111.1.2 Formation of H-Terminated Silicon Surfaces 30311.1.3 Stability of H-Terminated Silicon Surfaces 30411.1.4 Approach 30511.1.5 Outline 30511.2 Techniques Characterizing Wet Chemically Functionalized Surfaces 30711.2.1 X-Ray Photoelectron Spectroscopy 30711.2.2 Infrared Absorption Spectroscopy 30811.2.3 Secondary Ion Mass Spectrometry 31011.2.4 Surface-Enhanced Raman Spectroscopy 31111.2.5 Spectroscopic Ellipsometry 31111.2.6 X-Ray Reflectivity 31211.2.7 Contact Angle, Wettability 31211.2.8 Photoluminescence 31211.2.9 Electrical Measurements 31311.2.10 Imaging Techniques 31311.2.11 Electron and Atom Diffraction Methods 31311.3 Hydrosilylation of H-Terminated Surfaces 31411.3.1 Catalyst-Aided Reactions 31511.3.2 Photochemically Induced Reactions 31811.3.3 Thermally Activated Reactions 32011.4 Electrochemistry of H-Terminated Surfaces 32211.4.1 Cathodic Grafting 32211.4.2 Anodic Grafting 32311.5 Use of Halogen-Terminated Surfaces 32411.6 Alcohol Reaction with H-Terminated Si Surfaces 32711.7 Outlook 331Acknowledgments 331References 33212. Chemical Stability of Organic Monolayers Formed in Solution 339Leslie E. O’Leary, Erik Johansson, and Nathan S. Lewis12.1 Reactivity of H-Terminated Silicon Surfaces 33912.1.1 Background 33912.1.1.1 Synthesis of H-Terminated Si Surfaces 33912.1.2 Reactivity of H-Si 34212.1.2.1 Aqueous Acidic Media 34212.1.2.2 Aqueous Basic Media 34312.1.2.3 Oxygen-Containing Environments 34412.1.2.4 Alcohols 34412.1.2.5 Metals 34512.2 Reactivity of Halogen-Terminated Silicon Surfaces 34712.2.1 Background 34712.2.1.1 Synthesis of Cl-Terminated Surfaces 34812.2.1.2 Synthesis of Br-Terminated Surfaces 35012.2.1.3 Synthesis of I-Terminated Surfaces 35012.2.2 Reactivity of Halogenated Silicon Surfaces 35112.2.2.1 Halogen Etching 35112.2.2.2 Aqueous Media 35212.2.2.3 Oxygen-Containing Environments 35312.2.2.4 Alcohols 35512.2.2.5 Other Solvents 35612.2.2.6 Metals 35912.3 Carbon-Terminated Silicon Surfaces 36012.3.1 Introduction 36012.3.2 Structural and Electronic Characterization of Carbon-Terminated Silicon 36112.3.2.1 Structural Characterization of CH3-Si(111) 36212.3.2.2 Structural Characterization of Other Si-C Functionalized Surfaces 36212.3.2.3 Electronic Characterization of Alkylated Silicon 36412.3.3 Reactivity of C-Terminated Silicon Surfaces 36612.3.3.1 Thermal Stability of Alkylated Silicon 36712.3.3.2 Stability in Aqueous Conditions 36712.3.3.3 Stability of Si-C Terminated Surfaces in Air 37112.3.3.4 Stability of Si-C Terminated Surfaces in Alcohols 37212.3.3.5 Stability in Other Common Solvents 37212.3.3.6 Silicon–Organic Monolayer–Metal Systems 37412.4 Applications and Strategies for Functionalized Silicon Surfaces 37612.4.1 Tethered Redox Centers 37812.4.2 Conductive Polymer Coatings 37912.4.3 Metal Films 38212.4.3.1 Stability Enhancement 38212.4.3.2 Deposition on Organic Monolayers 38212.4.4 Semiconducting and Nonmetallic Coatings 38912.4.4.1 Stability Enhancement 38912.4.4.2 Deposition on Si by ALD 38912.5 Conclusions 391References 39213. Immobilization of Biomolecules at Semiconductor Interfaces 401Robert J. Hamers13.1 Introduction 40113.2 Molecular and Biomolecular Interfaces to Semiconductors 40213.2.1 Functionalization Strategies 40213.2.2 Silane Derivatives 40313.2.3 Phosphonic Acids 40613.2.4 Alkene Grafting 40613.3 DNA-Modified Semiconductor Surfaces 40713.3.1 DNA-Modified Silicon 40713.3.2 DNA-Modified Diamond 41113.3.3 DNA on Metal Oxides 41213.4 Proteins at Surfaces 41513.4.1 Protein-Resistant Surfaces 41513.4.2 Protein-Selective Surfaces 41713.5 Covalent Biomolecular Interfaces for Direct Electrical Biosensing 41813.5.1 Detection Methods on Planar Surfaces 41813.5.2 Sensitivity Considerations 42013.6 Nanowire Sensors 42213.7 Summary 422Acknowledgments 423References 42314. Perspective and Challenge 429Franklin (Feng) Tao and Steven L. BernasekIndex 431