Functionalization of Semiconductor Surfaces

444 Pages·2012·6.169 MB·English

FUNCTIONALIZATION OF
SEMICONDUCTOR
SURFACES
FUNCTIONALIZATION OF
SEMICONDUCTOR
SURFACES
Edited by
Franklin (Feng) Tao
University of Notre Dame, Notre Dame, Indiana
Steven L. Bernasek
Princeton University, Princeton, New Jersey
Copyright(cid:2)2012byJohnWiley&Sons,Inc.Allrightsreserved
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LibraryofCongressCataloging-in-PublicationData:
Functionalizationofsemiconductorsurfaces/editedbyFranklin(Feng)Tao,StevenL.Bernasek.
p.cm.
Includesindex.
ISBN978-0-470-56294-9(hbk.)
1.Semiconductors–Surfaces.2.Semiconductors–Materials.I.Tao,Franklin(Feng),
1971-II.Bernasek,S.L.(StevenL.)
QC611.6.S9F862012
5410.377–dc23
2011046737
PrintedintheUnitedStatesofAmerica
ISBN:9780470562949
10 9 8 7 6 5 4 3 2 1
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 ScanningTunnelingMicroscopyandAtomic
ForceMicroscopy 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
v
vi
CONTENTS
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-EdgeX-RayAbsorptionFineStructure
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(cid:2)1), Ge(100)-(2(cid:2)1), and Diamond(100)-(2(cid:2)1)
Surfaces 29
3.2.2 Si(111)-(7(cid:2)7) Surface 33
3.3 GeometryandElectronicStructureofH-Terminated
SemiconductorSurfaces 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
vii
CONTENTS
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 [2þ2] 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 [2þ2]-Like Cycloaddition on Si(111)-(7(cid:2)7) 61
4.3 [4þ2] 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 [4þ2]-Like Cycloaddition on Si(111)-(7(cid:2)7) 69
4.4 Cycloaddition of Unsaturated Organic Molecules Containing
One or More Heteroatom 71
4.4.1 C¼O-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
viii
CONTENTS
5.2.1 Thiophene, Furan, and Pyrrole on Si(111)-(7(cid:2)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(cid:2)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
ix
CONTENTS
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(cid:2)1) 165
7.2.1 Naphthalene and Anthracene on Si(100)-(2(cid:2)1) 165
7.2.2 Tetracene on Si(100)-(2(cid:2)1) 167
7.2.3 Pentacene on Si(100)-(2(cid:2)1) 169
7.2.4 Perylene on Si(100)-(2(cid:2)1) 172
7.2.5 Coronene on Si(100)-(2(cid:2)1) 173
7.2.6 Dibenzo[a,j]coronene on Si(100)-(2(cid:2)1) 174
7.2.7 Acenaphthylene on Si(100)-(2(cid:2)1) 175
7.3 PAHs on Si(111)-(7(cid:2)7) 176
7.3.1 Naphthalene on Si(111)-(7(cid:2)7) 176
7.3.2 Tetracene on Si(111)-(7(cid:2)7) 179
7.3.3 Pentacene on Si(111)-(7(cid:2)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,andTertiaryAmines
onSi(100)andGe(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
x
CONTENTS
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(cid:2)1) Surface 247
9.3.1 Attachment of 1,3-Butadiene to the Si(100)-(2(cid:2)1)
Surface 249
9.3.2 Attachment of 1,3-Cyclohexadiene to the
Si(100)-(2(cid:2)1) Surface 257
9.4 Reactions on the SiC(100)-(3(cid:2)2) Surface 263
9.5 Reactions on the SiC(100)-(2(cid: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(cid:2)1)–H 279
xi
CONTENTS
10.3.1.2 Long-Chain Alkenes on Si(100)-(2(cid:2)1)–H 284
10.3.1.3 Cross-Row Nanostructure 285
10.3.1.4 Aldehyde and Ketone: Acetophenone –
AUnique 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