Doping of Carbon Nanotubes (eBook)

Sergey Bulyarskiy received his PhD in 1976 and his doctor of science degree in 1989, becoming a professor in 1990. From 1991 to 2014 he served as the vice-rector of Ulyanovsk State University, Russia, and Head of the Department. Since 2014 he has been the Head of the Laboratory of Microelectronics Nanotechnologies, an Institute of the Russian Academy of Sciences. He was elected a Corresponding Member of the Academy of Sciences of the Republic of Tatarstan and was awarded various science prizes in Russia. Prof. Bulyarskiy currently pursues research on the theoretical foundations of nanotechnologies and nanoelectronics, physics, nanoelectronic devices, diagnostic quality and reliability prediction. He has obtained important results on the development of thermodynamic and kinetic models for the self-organization of nanoelements in multicomponent systems of semiconductors and carbon. He is currently working at the Russian Academy of Sciences in Moscow, studying problems in carbon nanotubes and grapheme. S. Bulyarskiy directs the school of young scientists in “Physical problems of nanotechnology, nanoelectronics components and microstructures” and is Chairman of the Organizing Committee of the annual International Conference “Opto-, nanoelectronics, nanotechnology and micro.” He has authored more than 200 scientific papers and 20 monographs. Alexander Saurov received his PhD in 1988 and his Doctor of Science degree in 1999, becoming a professor in 2001 and Corresponding Member of the Russian Academy of Sciences in 2008, elected a Full Member of the Russian Academy of Sciences in 2016. Since 2009 he has been the Director of the Institute of Microelectronics Nanotechnologies of the Russian Academy of Sciences (INME RAS), Moscow. A specialist for integral circuit, micro- and nanosystems, he has authored 161 scientific publications and holds 40 patents. Prof. Saurov’s main findings concern: the development of technologies of ultra-small sizes of integrated structures, very-large-scale integration (VLSI) and microsystems on the basis of non-lithographic constructive-technological methods of autoshaping, technologies of self-aligned integrated transistor configurations and integrated microsensors, low-swirl injectors (LSIs) with ultra-low energy, and microsensors on the basis of silicon-carbon nanotechnologies. He is a senior editor of the journal “Nanoindustry” and a member of the editorial board of the magazine “Microsystems engineering”.

Preface 6
Contents 8
Contributors 12
Abstract 13
1 Adsorption and Doping as Methods for the Electronic Regulation Properties of Carbon Nanotubes 14
Abstract 14
References 18
2 Thermodynamics and Kinetics of Adsorption and Doping of a Graphene Plane of Carbon nanotubes and Graphene 20
Abstract 20
2.1 The Equilibrium of Thermodynamic Systems 21
2.2 Thermodynamic and Kinetic Approaches to the Description of Thermodynamic Systems 24
2.2.1 Kinetics Equations 24
2.2.2 Solutions of Equations of Physical Kinetics 25
2.2.3 The Kinetic Coefficients 26
2.2.4 Kinetic Processes in Carbon Nanostructures 28
2.2.5 Role and Limits of the Thermodynamic Approach with Regard to the Process of Doping Carbon Nanostructures 28
2.3 Description of Defect Formation in Crystals 29
2.3.1 The Quasi-chemical Reaction Method 29
2.3.2 The Gibbs Free Energy Search Minimum Method 32
2.4 The Thermodynamics of Physical Adsorption of Carbon Nanotubes and Graphene 32
2.4.1 Objects of Research: CNTs and Graphene 33
2.4.2 Differences Between Physical and Chemical Adsorption 33
2.4.3 The Conservation Law of Place Number 35
2.4.4 The Laws of Conservation of Particle Number 36
2.4.5 Free Energy of the Systems 36
2.5 The Thermodynamics of Doping and Chemical Adsorption 40
2.5.1 The Conservation Laws for the Number of Places 40
2.5.2 The Conservation Laws of Particle Number 41
2.5.3 The Conservation Law of Charge 41
2.6 Kinetics of Doping Carbon Nanotubes and Graphene 46
2.7 Kinetics of the Desorption Process 48
2.8 The Thermodynamics and Kinetics of Chemical Vapor Deposition Growth of Carbon Nanotubes 51
2.8.1 Catalyst Nanoparticles 52
2.8.2 The Free Energy of the Particles 53
2.8.3 The Laws of Conservation for the Number of Sites and Particles 54
2.8.4 Calculation of the Cluster Size Distribution 55
2.8.5 The Kinetics of the Growth of a Nanotube 59
2.8.6 Some Experimental Results 60
2.8.7 System of Kinetic Equations 61
2.9 Conclusion 67
References 68
3 Interaction of Hydrogen with a Graphene Plane of Carbon Nanotubes and Graphene 70
Abstract 70
3.1 Adsorption by Carbon Nanotubes as a Basis for Hydrogen Storage Technology 71
3.2 Quantum Mechanical Calculations of Carbon Nanotube Adsorptive Characteristics 76
3.3 Modeling of Single Carbon Nanotube Properties for the Processes of Hydrogen Adsorption 78
3.4 Thermodynamic Evaluations for Limiting Hydrogen Adsorption by SWCNTs 91
3.5 Hydrogen Desorption Kinetics (TGA) 96
3.6 Experimental Studies of Hydrogen Adsorption on SWCNTs 99
3.7 Modeling of a Nanotube with Stone–Wales Defects 104
3.8 The Problem of Hydrogen Storage 106
3.9 Conclusion 109
References 109
4 Oxygen Interaction with Electronic Nanotubes 115
4.1 Simulation of the Oxygen Interaction with Electronic Nanotubes 115
4.2 The Characteristic Parameters of Oxygen Adsorption 120
4.3 Conclusion 123
References 124
5 Nitrogen Interaction with Carbon Nanotubes: Adsorption and Doping 126
Abstract 126
5.1 Nitrogen Arrangement on Carbon Nanotubes 127
5.2 Determination of Nitrogen Atom Configuration on the Graphene Plane of a Carbon Nanotube 130
5.3 Analysis of Atomic Configurations and Nitrogen Electronic States on Graphene Planes of CNTs by Quantum Mechanical Methods 133
5.4 Simulation of Nitrogen Chemisorption on Single-Wall Carbon Nanotubes 135
5.5 Nitrogen Chemisorption Simulation for Nanotubes with Stone-Wales Defects 138
5.6 Thermodynamics of the Nitrogen Physical Adsorption Processes on Carbon Nanotubes 141
5.7 Thermodynamics of Carbon Nanotube Doping by Nitrogen 143
5.7.1 The Laws of Conservation of Place Number 146
5.7.2 The Laws of Conservation of Particle Number 147
5.7.3 The Law Charge Conservation 147
5.7.4 Configuration Entropy of the System 147
5.8 Calculations of Doped Carbon Nanotube Conductance 155
5.9 Analysis of Thermogravimetric Curves of Carbon Nanotubes, Doped by Nitrogen 155
5.10 Calculation of Nitrogen Fugacity Under Plasmochemical Synthesis 159
5.10.1 The Place Number Conservation Laws 161
5.10.2 The Particles Number Conservation Laws 161
5.10.3 Charge Conservation Law 162
5.10.4 Free Energy of the System 162
5.11 Analysis of X-Ray Photoelectron Spectra of Nitrogen Doped Carbon Nanotubes 166
5.12 Applications of Nitrogen Doped Carbon Nanotubes 169
5.12.1 Improvement of Emissive Properties 169
5.12.2 Electrodes for Ionic-Lithium Batteries 170
5.13 Conclusion 171
References 171
6 Carbon Nanotube Doping by Acceptors. The p–? Junction Formation 181
Abstract 181
6.1 The Electronic Properties of Boron-Doped Nanotubes 181
6.2 Technology and Thermodynamics of Boron-Doped Carbon Nanotubes 182
6.3 Boron-Doped Carbon Nanotube Usage 183
6.4 The p–? Junction Forming Carbon Nanotubes 184
6.4.1 Features of p–n Junction Formation in Carbon Nanotubes by a Mutual Acceptors and Donor Doping 186
6.4.2 Carbon Nanotube Arrays as a Volume Crystal Analog 188
6.4.3 The Formation of a p–n Junction, Under Changing Temperatures, in a Nitrogen-Doped Carbon Nanotube Array 189
6.4.4 Doping Admixture Change During the Growth Process 189
6.4.5 Ionic Doping of an Array 189
6.4.6 Carbon Nanotube Array Oxidation Under Ultraviolet Irradiation 190
6.5 Summary 190
References 191
Conclusions 193
What Was Known in the Field Before the Book Was Written? 193
What Was Identified Whilst Writing the Book? 193
What is Clear After Completion of Writing the Book? 194
What Lies Ahead in this Field? 194
Index 195