This book presents both fundamental knowledge and latest achievements of this rapidly growing field in the last decade. It presents a complete and concise picture of the the state-of-the-art in the field, encompassing the most active international research groups in the world. Led by contributions from leading global research groups, the book discusses the functionalization of semiconductor surface. Dry organic reactions in vacuum and wet organic chemistry in solution are two major categories of strategies for functionalization that will be described. The growth of multilayer-molecular architectures on the formed organic monolayers will be documented. The immobilization of biomolecules such as DNA on organic layers chemically attached to semiconductor surfaces will be introduced. The patterning of complex structures of organic layers and metallic nanoclusters toward sensing techniques will be presented as well.
Table of Contents:
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 Junction 292
10.3.2.2 One-Dimensional Heterojunction 295
10.3.3 UPS of 1D Nanostructures on the Surface 296
10.4 Conclusions 298
Acknowledgment 299
References 299
11. Formation of Organic Monolayers Through Wet Chemistry 301
Damien Aureau and Yves J. Chabal
11.1 Introduction, Motivation, and Scope of Chapter 301
11.1.1 Background 301
11.1.2 Formation of H-Terminated Silicon Surfaces 303
11.1.3 Stability of H-Terminated Silicon Surfaces 304
11.1.4 Approach 305
11.1.5 Outline 305
11.2 Techniques Characterizing Wet Chemically Functionalized Surfaces 307
11.2.1 X-Ray Photoelectron Spectroscopy 307
11.2.2 Infrared Absorption Spectroscopy 308
11.2.3 Secondary Ion Mass Spectrometry 310
11.2.4 Surface-Enhanced Raman Spectroscopy 311
11.2.5 Spectroscopic Ellipsometry 311
11.2.6 X-Ray Reflectivity 312
11.2.7 Contact Angle, Wettability 312
11.2.8 Photoluminescence 312
11.2.9 Electrical Measurements 313
11.2.10 Imaging Techniques 313
11.2.11 Electron and Atom Diffraction Methods 313
11.3 Hydrosilylation of H-Terminated Surfaces 314
11.3.1 Catalyst-Aided Reactions 315
11.3.2 Photochemically Induced Reactions 318
11.3.3 Thermally Activated Reactions 320
11.4 Electrochemistry of H-Terminated Surfaces 322
11.4.1 Cathodic Grafting 322
11.4.2 Anodic Grafting 323
11.5 Use of Halogen-Terminated Surfaces 324
11.6 Alcohol Reaction with H-Terminated Si Surfaces 327
11.7 Outlook 331
Acknowledgments 331
References 332
12. Chemical Stability of Organic Monolayers Formed in Solution 339
Leslie E. O’Leary, Erik Johansson, and Nathan S. Lewis
12.1 Reactivity of H-Terminated Silicon Surfaces 339
12.1.1 Background 339
12.1.1.1 Synthesis of H-Terminated Si Surfaces 339
12.1.2 Reactivity of H-Si 342
12.1.2.1 Aqueous Acidic Media 342
12.1.2.2 Aqueous Basic Media 343
12.1.2.3 Oxygen-Containing Environments 344
12.1.2.4 Alcohols 344
12.1.2.5 Metals 345
12.2 Reactivity of Halogen-Terminated Silicon Surfaces 347
12.2.1 Background 347
12.2.1.1 Synthesis of Cl-Terminated Surfaces 348
12.2.1.2 Synthesis of Br-Terminated Surfaces 350
12.2.1.3 Synthesis of I-Terminated Surfaces 350
12.2.2 Reactivity of Halogenated Silicon Surfaces 351
12.2.2.1 Halogen Etching 351
12.2.2.2 Aqueous Media 352
12.2.2.3 Oxygen-Containing Environments 353
12.2.2.4 Alcohols 355
12.2.2.5 Other Solvents 356
12.2.2.6 Metals 359
12.3 Carbon-Terminated Silicon Surfaces 360
12.3.1 Introduction 360
12.3.2 Structural and Electronic Characterization of Carbon-Terminated Silicon 361
12.3.2.1 Structural Characterization of CH3-Si(111) 362
12.3.2.2 Structural Characterization of Other Si-C Functionalized Surfaces 362
12.3.2.3 Electronic Characterization of Alkylated Silicon 364
12.3.3 Reactivity of C-Terminated Silicon Surfaces 366
12.3.3.1 Thermal Stability of Alkylated Silicon 367
12.3.3.2 Stability in Aqueous Conditions 367
12.3.3.3 Stability of Si-C Terminated Surfaces in Air 371
12.3.3.4 Stability of Si-C Terminated Surfaces in Alcohols 372
12.3.3.5 Stability in Other Common Solvents 372
12.3.3.6 Silicon–Organic Monolayer–Metal Systems 374
12.4 Applications and Strategies for Functionalized Silicon Surfaces 376
12.4.1 Tethered Redox Centers 378
12.4.2 Conductive Polymer Coatings 379
12.4.3 Metal Films 382
12.4.3.1 Stability Enhancement 382
12.4.3.2 Deposition on Organic Monolayers 382
12.4.4 Semiconducting and Nonmetallic Coatings 389
12.4.4.1 Stability Enhancement 389
12.4.4.2 Deposition on Si by ALD 389
12.5 Conclusions 391
References 392
13. Immobilization of Biomolecules at Semiconductor Interfaces 401
Robert J. Hamers
13.1 Introduction 401
13.2 Molecular and Biomolecular Interfaces to Semiconductors 402
13.2.1 Functionalization Strategies 402
13.2.2 Silane Derivatives 403
13.2.3 Phosphonic Acids 406
13.2.4 Alkene Grafting 406
13.3 DNA-Modified Semiconductor Surfaces 407
13.3.1 DNA-Modified Silicon 407
13.3.2 DNA-Modified Diamond 411
13.3.3 DNA on Metal Oxides 412
13.4 Proteins at Surfaces 415
13.4.1 Protein-Resistant Surfaces 415
13.4.2 Protein-Selective Surfaces 417
13.5 Covalent Biomolecular Interfaces for Direct Electrical Biosensing 418
13.5.1 Detection Methods on Planar Surfaces 418
13.5.2 Sensitivity Considerations 420
13.6 Nanowire Sensors 422
13.7 Summary 422
Acknowledgments 423
References 423
14. Perspective and Challenge 429
Franklin (Feng) Tao and Steven L. Bernasek
Index 431
