Science of Fullerenes and Carbon Nanotubes

Transcription

1 Science of Fullerenes and Carbon Nanotubes M. S. DRESSELHAUS Department of Electrical Engineering and Computer Science and Department of Physics Massachusetts Institute of Technology, Cambridge, Massachusetts G. DRESSELHAUS Francis Bitter National Magnet Laboratory Massachusetts Institute of Technology, Cambridge, Massachusetts P C. EKLUND Department ofphysics and Astronomy and Centerfor Applied Energy Research University of Kentucky, Lexington, Kentucky ACADEMIC PRESS An Imprint of Elscvfer San Diego Boston New York London Sydney Tokyo Toronto

2 Contents Preface xvii CHAPTER I Historical Introduction Early History Astronomical Observations Carbon Cluster Studies , Recent History S. Architectural Analogs Biological and Geological Examples Road Map References CHAPTER 2 Carbon Materials General Considerations Graphite Graphite Materials Graphite Whiskers Carbon Fibers Glassy Carbon Carbon Blacks Carbon Coated Carbide Particles Carbynes Carbolites Amorphous Carbon

3 Vi Contents Porous Carbons Liquid Carbon., Graphite Intercalation Compounds Diamond Other Diamond Materials Chemical Vapor Deposited Diamond Films Diamond-like Carbon Films Diamond-like and Cage Hydrocarbon Molecules Synthesis of a Fully Unsaturated, All-Carbon Polymer Metallo-Carbohedrenes (Met-Cars) Carbon-Free Fullerenes Metal-Coated Fullerenes References CHAPTER 3 Structure of Fullerenes,., Structure of C1w and Euler's Theorem Structure of C70 and Higher Fullerenes The Projection Method for Specifying Fullerenes References CHAPTER 4 Symmetry Considerations of Fullerene Molecules SQ 4.1. lcosahedral Symmetry Operations Symmetry of Vibrational Modes Symmetry for Electronic States , Going from Higher to Lower Symmetry Symmetry Considerations for C Symmetry Considerations for Higher-Mass Fullerenes Symmetry Considerations for Isotopic Effects References CHAPTER 5 Synthesis, Extraction, and Purification of Fullerenes...,,., Synthesis of Fulierenes......,.,.., Historical Perspective , Synthesis Details.....,.,...,,.,,, Fullerene Extraction.....,.,..,..,,,,,., Solvent Methods.....,,.,.,.,,,,.,, 116 5,2.2. Sublimation Methods..,....,,,..,,,., Solubility of Fullerenes in Solvents Fullerene Purification,.,..,.,.,,,...,,, Solvent Methods......,...,.,...,., 121

4 Contents Vll Sublimation in a Temperature Gradient Gas-Phase Separation and Purification Vaporization Studies of C Endohedral Fullerene Synthesis Health and Safety Issues References CHAPTER 6 Fullerene Growth, Contraction, and Fragmentation Fullerene Growth Models Stone-Wales Model Model for C2 Absorption or Desorption Nllerene Growth from a Corannulene Cluster Transition from C6o to C Mass Spectrometry Characterization Stability Issues Fullerene Contraction and Fragmentation Photofragmentation Collision of Fullerene Ion Projectiles , Collision of Fullerene Ions with Surfaces Fragmentation of C60 by Energetic Ions Molecular Dynamics Models References CHAPTER 7 Crystalline Structure of Fullerenc Solids Crystalline C6o Ambient Structure Group Theory for Crystalline Phases LowTemperature Phases Merohedral Disorder Model for Phase Transitions in C6o Crystalline C70 and Higher-Mass Fullerenes Effect of Pressure on Crystal Structure Effect of Temperature on Crystal Structure Polymerized Ftitllerenes Photopolymerization of C6o Electron Beam-Induced Polymerization of C6o Pressure-Induced Polymerization of C6o Plasma-Induced Polymerization of C6o Photopolymerization of C70 Films References

5 viii Contents CHAPTER8 Classification and Structure of Doped Fullerenes Classification of Types of Doping for Fullerenes....,..., Endohedral Doping Substitutional Doping Exohedral Doping Exohedral Charge Transfer Compounds.., , Exohedral Ciathrate C6o Compounds , Positron Exohedral Trapping Structure of Alkali Metal-Doped C60 Crystals M3Cdn Alkali Metal Structures M I C6n, M4C60, and M6C6o Structures (M = K, Rb, Cs) ,5.3. NaXC6o Structures Structures for MZM1 C6o and Related Compounds Structure of Ammoniated M3C6o Compounds Structure of Alkaline Earth-Doped C6o Ca,,C6o Structure SrxC6a and Ba,C 6o Structures , , Rare Earth RxC60 Structures Structure of Other Crystalline Fulleride Phases Halogen-Doped Fhllerenes Fullerene Epoxides and Related Compounds TDAE--C6o Metal-C60 Multilayer Structures , The Doping of C70 and Higher-Mass Fullerenes...., References ,....., CHAPTER 9 Single-Crystal and Epitaxial Film Growth Single-Crystal Growth Synthesis of Large C 6o and C oo Crystals by Vapor Growth Thin-Film Synthesis Epitaxial C6o Films Free-Standing C6 o Films, or Fullerene Membranes Synthesis of Doped C6o Crystals and Films Charge 'transfer Compounds Based on Alkali Metals and Alkaline Earths Fullerene-Based Clathrate Materials....., References CHAPTER 10 Fullerene Chemistry and Electrochemistry Practical Considerations in Fullerene Derivative Chemistry General Characteristics of Fullerene Reactions

6 Contents Reduction and Oxidation of C60 and Coo Fullerene Reduction-General Remarks ,2, Electrochemical Fullerene Reduction and Oxidation Chemical Oxidation of C Hydrogenation, Alkylation, and Amination Halogenation Reactions , Bridging Reactions..., Cycioaddition Reactions , Substitution Reactions , Reactions with Free Radicals , Host-Guest Complexes and Polymerization Host--Guest Complexes ,10.2. Polymerization References CHAPTER 11 Vibrational Modes Overview of Mode Classifications...., Experimental Techniques, C60 Intramolecular Modes The Role of Symmetry and Theoretical Models Theoretical Crystal Field Perturbation of the Intramolecular Modes of C Isotope Effects in the Vibrational and Rotational Spectra of C60 Molecules Intermolecular Modes , Experimental Results on C60 Solids and Films Raman-Active Modes , Infrared-Active Modes Higher-Order Raman Modes in C Higher-Order Infrared Modes in C Isotope Effects in the Raman Spectra Silent Intramolecular Modes in C Luminescence Studies of Vibrations in CGo Neutron Scattering HREELS Study of Vibrational Modes Vibrational Modes as a Probe of Phase Transitions ]. Vibrational States Associated with Excited Electronic States Vibrational Modes in Doped Fullerene Solids Doping Dependence of Raman-Active Modes Doping Dependence of the Fl,,-Derived Intramolecular Modes Other Doping-Dependent Intramolecular Effects Doping-Dependent Intermolecular Effects

7 Contents Vibrational Spectra for C70 and Higher Fullerenes Intermolecular Vibrational Spectra for C,ra Intermolecular Vibrational Spectra for qo., Vibrational Modes in Doped C70 Solids Vibrational Spectra for Phototransformed Fullerenes Vibrational Spectra for C6o under Pressure Vibrational Spectra of Other Fullerene-Related Materials References , , CHAPTER 12 Electronic Structure..,., Electronic Levels for Free C6o Molecules Models for Molecular Orbitals ,2. Level Filling for Free Electron Model..., Symmetry-Based Models Many-Electron States for C6a and Other Icosahedral Fullerenes Multiplet States for Free Ions C6o..., , Ground States for Free Ions CZa± Excited States for Negative Molecular irons C6" ,3. Positive Molecular Ions CLO ,5. Excitonic States for C6a , Molecular States for Higher-Mass Fullerenes,,.,, , Molecular States for C Metallofullerenes.....,.,., Electronic Structure of Fullerenes in the Solid State....., Overview of the Electronic Structure in the Solid State Band Calculations for Solid C6o,...., Band Calculations for Alkali Metal-Doped C60.., Electronic Structure of Alkaline Earth-Doped C6o ,5. Band Calculations for Other Doped Fullerenes Band Calculations for Other Fullerenes...,..., Many-Body Approach to Solid C6o...,..,, References, ,,.,.,,,,., CHAPTER 13 Optical Properties,.,...,.,.,,.,,,,,,,., Optical Response of Isolated C6a Molecules..,......, Introduction to Molecular Photophysics.,..., Dipole-Allowed Transitions , Optical Transitions between Low-Lying HerzbergTeller Vibronic States.,....,....,.., Optical Studies of C6e in Solution, ,,, Absorption of C6o in Solution Photoluminescence of C6o in Solution , 480

8 Dynamics of Excited States in Isolated C60 Molecules Optically Detected Magnetic Resonance (ODMR) for Molecules, Optical Properties of Solid C Overview ,3.2. Optical Absorption in C60 Films , Low-Frequency Dielectric Properties , Optical Transitions in Phototransformed C6Q Optical Properties of Doped C6Q Optical Absorption of C6Q Anions in Solution Optical Properties of M6Ca Normal State Optical Properties of M3C Superconducting State Optical Properties Optical Properties of MIC60 Compounds.., Optical Properties of C60-Polymer Composites ,6. Optical Properties of Higher-Mass Fullerenes Optical Properties of C Dynamic and Nonlinear Optical Properties of Fullerenes Dynamcal Properties Nonlinear Absorption Effects References......, CHAPTER 14 Transport and Thermal Properties Electrical Conductivity ,1, Dependence on Stoichiometry Temperature Dependence ,1.3. Alkaline Earth-Doped C6o Alkali Metal-Doped C Transport in Metal-C60 Multilayer Structures Lewis Acid-Doped C6Q Electron-Phonon Interaction Special Properties of Fullerenes Magnitudes of the Coupling Constant Symmetry Considerations Jahn-Teller Effects.., , Hall Coefficient...., Magnetoresistance , Electronic Density of States Pressure Effects Photoconductivity Specific Heat Temperature Dependence , Specific Heat for qr0....., , Specific Heat for I<3C

9 xii Contents Scanning Calorimetry Studies Temperature Coefficient of Thermal Expansion, ,11, Thermal Conductivity Thermopower., Internal Friction.., References.., ,., CHAPTER 1S Superconductivity Experimental Observations of Superconductivity Critical Temperature Magnetic Field Effects Temperature Dependence of the Superconducting Energy Gap Isotope Effect Pressure-Dependent Effects Mechanism for Superconductivity References.., , CHAPTER 16 Magnetic Resonance Studies , Nuclear Magnetic Resonance , ,1.1. Structural Information about the Molecular Species ,2. Bond Lengths Structural Information about Dopant Site Locations ,1.4. Molecular Dynamics in C60 and C , Stoichiornetric Characterization of M,C 6n Phases Knight Shift and the Metallic Phase of M3C6o, Density of States Determination by NMR Determination of Superconducting Gap by NMR..,, NMR Studies of Magnetic Fullerenes Electron Paramagnetic Resonance , EPR Studies of Endohedrally Doped Fullerenes EPR Studies of Neutral C60 and Doped C , Tinie-Resolved EPR Study of Triplet State of Fullerenes , EPR Studies of Strong Paramagnets....., Muon Spin Resonance (,,SR) ,., References......, , CHAPTER 17 Surface Science Studies Related to Fullerenes...,.,.,,, ,1. Photoemission and Inverse Photoemission..,,.., , UV Spectra for C6o , XPS Spectra for Cso ,.,

10 Contents xiii. 17,1.3. PES and IPES Spectra for Doped Fullerenes XPS Studies of Adsorbed Fullerenes on Substrates Electron Energy Loss Spectroscopy , Elastic Electron Scattering and Low-Energy Electron Diffraction Studies Electronic Transitions near the Fermi Level Core Level Studies Plasmon Studies HREELS and Vibrational Spectra EELS Spectra for Alkali Metal-Doped Fullerenes Auger Electron Spectroscopy.., ,, Scanning Tunneling Microscopy STM Studies of the Fullerene-Surface Interaction, Atomic Force Microscope Studies Temperature-Prograrnmed Desorption Work Function Surface-Enhanced Raman Scattering Photoionization Fullerene Interface Interactions with Substrates C60 on Noble Metal Surfaces C60 on Transition Metal Surfaces C60 on Si Substrates C60 on GaAs Higher-Mass Fullerenes on Various Substrates Metallofullerenes Adsorbed on Surfaces References CHAP'T'ER 18 Magnetic Properties Diamagnetic Behavior Magnetic Endohedral and Exohedral Dopants.., Magnetic Properties of Fullerene Ions Pauli Paramagnetism in Doped Fullerenes p-level Magnetism Observations in Alkali Metal-Doped C60.., Observations in TDAE-C References , CHAPTER 19 C60-Related 1bbules and Spherules Relation between Tubules and Fullerenes Experimental Observation of Carbon Nanotubes Observation of Multiwall Carbon Nanotubes Observation of SingleWall Carbon Nanotubes

11 Xiv Contents., Tubule Caps and Chirality....., Carbon Nanocones Nanotube Synthesis, Alignment of Nanotubes , Growth Mechanism ,4. Symmetry Properties of Carbon Nanotubes., Specification of Lattice Vectors in Real Space Symmetry for Symmorphic Carbon Tubules.., Symmetry for Nonsymmorphic Carbon Tubules Reciprocal Lattice Vectors Electronic Structure: Theoretical Predictions....., , SingleWall Syrnmorphic 'tubules Single-Wall Nonsymmorpbic Chiral Tubules Multiwall Nanotubes and Arrays , D Electronic Structure in a Magnetic Field Electronic Structure : Experimental Results X, Scanning Tunneling Spectroscopy Studies Transport Measurements Magnetoresistance Studies Magnetic Susceptibility Studies Electron Energy Loss Spectroscopy Studies Phonon Modes in Carbon Nanotubes ,7.1. Phonon Dispersion Relations....., , Calculated Raman- and Infrared-Active Modes Experiments on Vibrational Spectra of Carbon Nanotubes ,8. Elastic Properties...,.,,.....,,.., ,9. Filled Nanotubes, ,10, Onion-Like Graphitic Particles , Possible Superconductivity in C 6o -Related Tubules References, , ,. 864 CHAPTER 20 Applications of Carbon Nanostructures.,..,....,.,,., ,1. Optical Applications , Optical Limiter...,,.,...,.,.,.,, , Photoexcited Cco--Polymer Composites....,.., Photorefractivity in C60-Polymer Composites , Electronics Applications......,...,,,...., Co Transistors ,,,.,.,,,,,, C60-Based Heterojunction Diodes..,,.,.,.,, C60 Polymer Composite Heterojunction Rectifying Diode C60-Polymer Composite Heterojunction Photovoltaic Devices......, , Microelectronic Fabrication and Photoresists,...,, ,2,6. Silicon Wafer Bonding,.,,..,. 889

12 Passivation of Reactive Surfaces Fullerenes Used for Uniform Electric Potential Surfaces Materials Applications Enhanced Diamond Synthesis Enhanced SiC Film Growth and Patterning Catalytic Properties of C Self-Assembled Monolayers New Chemicals Electrochemical Applications of Co Hydrogen Storage and Primary Batteries C5q Electrodes for Secondary Batteries Other Applications Nanotechnology Fullerene Coatings for STM Tips Fullerene Membranes Tribology-Lubricants Separations Sensors Commercialization and Patents References Index