CONTENTS
Franklin (Feng) Tao, Yuan Zhu, and Steven L. Bernasek
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
2. Surface Analytical Techniques
Ying Wei Cai and Steven L. Bernasek
2.2.1 Low-Energy Electron Diffraction
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
2.3.4.2 High-Resolution Electron Energy Loss Spectroscopy
2.3.5 Synchrotron-Based Methods
2.3.5.1 Near-Edge X-Ray Absorption Fine Structure Spectroscopy
2.3.5.3 Glancing Incidence X-Ray Diffraction
2.4 Kinetic and Energetic Probes
2.4.1 Thermal Programmed Desorption
3. Structures of Semiconductor Surfaces and Origins of Surface Reactivity with Organic Molecules
3.2 Geometry, Electronic Structure, and Reactivity of Clean Semiconductor Surfaces
3.2.1 Si(100)-(2×1), Ge(100)-(2×1), and Diamond(100)-(2×1) Surfaces
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
3.3.4 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
4. Pericyclic Reactions of Organic Molecules at Semiconductor Surfaces
Keith T. Wong and Stacey F. Bent
4.2 [2+2] Cycloaddition of Alkenes and Alkynes
4.2.5 [2+2]-Like Cycloaddition on Si(111)-(7×7)
4.3 [4+2] Cycloaddition of Dienes
4.3.1 1,3-Butadiene and 2,3-Dimethyl-1,3-Butadiene
4.3.4 [4+2]-Like Cycloaddition on Si(111)-(7×7)
4.4 Cycloaddition of Unsaturated Organic Molecules Containing One or More Heteroatom
4.4.1 C=O-Containing Molecules
4.4.3 Isocyanates and Isothiocyanates
5. Chemical Binding of Five-Membered and Six-Membered Aromatic Molecules
Franklin (Feng) Tao and Steven L. Bernasek
5.2 Five-Membered Aromatic Molecules Containing One Heteroatom
5.2.1 Thiophene, Furan, and Pyrrole on Si(111)-(7×7)
5.2.2 Thiophene, Furan, and Pyrrole on Si(100) and Ge(100)
5.3 Five-Membered Aromatic Molecules Containing Two Different Heteroatoms
5.4.1 Different Binding Configurations on (100) Face of Silicon and Germanium
5.4.2 Di-Sigma Binding on Si(111)-(7×7)
5.5 Six-Membered Heteroatom Aromatic Molecules
5.6 Six-Membered Aromatic Molecules Containing Two Heteroatoms
6.2 Multifunctional Aromatic Reactions on Clean Silicon Surfaces
6.2.1 Homoaromatic Compounds Without Additional Functional Groups
6.2.2 Functionalized Aromatics
6.2.3 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
6.2.6 Delivery of Aromatic Compounds onto Protected Silicon Substrates
7. Covalent Binding of Polycyclic Aromatic Hydrocarbon Systems
7.2.1 Naphthalene and Anthracene on Si(100)-(2×1)
7.2.2 Tetracene on Si(100)-(2×1)
7.2.3 Pentacene on Si(100)-(2×1)
7.2.4 Perylene on Si(100)-(2×1)
7.2.5 Coronene on Si(100)-(2×1)
7.2.6 Dibenzo[a, j] coronene on Si(100)-(2×1)
7.2.7 Acenaphthylene on Si(100)-(2×1)
7.3.1 Naphthalene on Si(111)-(7×7)
7.3.2 Tetracene on Si(111)-(7×7)
7.3.3 Pentacene on Si(111)-(7×7)
8. Dative Bonding of Organic Molecules
Young Hwan Min, Hangil Lee, Do Hwan Kim, and Sehun Kim
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)
8.2.1.1 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)
8.2.2.1 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
8.2.3.1 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)
8.2.4.1 Thiophene on Si(100) and Ge(100)
8.3 Dative Bonding of Lewis Acids (Electrophilic)
9. Ab Initio Molecular Dynamics Studies of Conjugated Dienes on Semiconductor Surfaces
Mark E. Tuckerman and Yanli Zhang
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)-(2×1) Surface
9.3.1 Attachment of 1,3-Butadiene to the Si(100)-(2×1) Surface
9.3.2 Attachment of 1,3-Cyclohexadiene to the Si(100)-(2×1) Surface
9.4 Reactions on the SiC(100)-(3×2) Surface
9.5 Reactions on the SiC(100)-(2×2) Surface
9.6 Calculation of STM Images: Failure of Perturbative Techniques
10. Formation of Organic Nanostructures on Semiconductor Surfaces
Md. Zakir Hossain and Maki Kawai
10.3.1 Individual 1D Nanostructures on Si(100)–H: STM Study
10.3.1.1 Styrene and Its Derivatives on Si(100)-(2×1)–H
10.3.1.2 Long-Chain Alkenes on Si(100)-(2×1)–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
11. Formation of Organic Monolayers Through Wet Chemistry
Damien Aureau and Yves J. Chabal
11.1 Introduction, Motivation, and Scope of Chapter
11.1.2 Formation of H-Terminated Silicon Surfaces
11.1.3 Stability of H-Terminated Silicon Surfaces
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
11.2.7 Contact Angle, Wettability
11.2.9 Electrical Measurements
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
11.4 Electrochemistry of H-Terminated Surfaces
11.5 Use of Halogen-Terminated Surfaces
11.6 Alcohol Reaction with H-Terminated Si Surfaces
12. Chemical Stability of Organic Monolayers Formed in Solution
Leslie E. O'Leary, Erik Johansson, and Nathan S. Lewis
12.1 Reactivity of H-Terminated Silicon Surfaces
12.1.1.1 Synthesis of H-Terminated Si Surfaces
12.1.2.3 Oxygen-Containing Environments
12.2 Reactivity of Halogen-Terminated Silicon Surfaces
12.2.1.1 Synthesis of Cl-Terminated Surfaces
12.2.1.2 Synthesis of Br-Terminated Surfaces
12.2.1.3 Synthesis of I-Terminated Surfaces
12.2.2 Reactivity of Halogenated Silicon Surfaces
12.2.2.3 Oxygen-Containing Environments
12.3 Carbon-Terminated Silicon Surfaces
12.3.2 Structural and Electronic Characterization of Carbon-Terminated Silicon
12.3.2.1 Structural Characterization of CH3–Si(111)
12.3.2.2 Structural Characterization of Other Si–C Functionalized Surfaces
12.3.2.3 Electronic Characterization of Alkylated Silicon
12.3.3 Reactivity of C-Terminated Silicon Surfaces
12.3.3.1 Thermal Stability of Alkylated Silicon
12.3.3.2 Stability in Aqueous Conditions
12.3.3.3 Stability of Si–C Terminated Surfaces in Air
12.3.3.4 Stability of Si–C Terminated Surfaces in Alcohols
12.3.3.5 Stability in Other Common Solvents
12.3.3.6 Silicon-Organic Monolayer-Metal Systems
12.4 Applications and Strategies for Functionalized Silicon Surfaces
12.4.2 Conductive Polymer Coatings
12.4.3.1 Stability Enhancement
12.4.3.2 Deposition on Organic Monolayers
12.4.4 Semiconducting and Nonmetallic Coatings
12.4.4.1 Stability Enhancement
12.4.4.2 Deposition on Si by ALD
13. Immobilization of Biomolecules at Semiconductor Interfaces
13.2 Molecular and Biomolecular Interfaces to Semiconductors
13.2.1 Functionalization Strategies
13.3 DNA-Modified Semiconductor Surfaces
13.4.1 Protein-Resistant Surfaces
13.4.2 Protein-Selective Surfaces
13.5 Covalent Biomolecular Interfaces for Direct Electrical Biosensing
13.5.1 Detection Methods on Planar Surfaces
13.5.2 Sensitivity Considerations