Electrodeposition of Nanostructured Materials (eBook)

Preface 6
Contents 9
1 An Overview of Nanostructured Materials 13
Abstract 13
1.1 Introduction to Materials Science 13
1.2 Physics of Solid State Materials 14
1.2.1 Atoms and the Periodic Table of Elements 14
1.2.2 Atomic Bonds and Condensed Matter 17
1.2.2.1 Inert Gas (van der Waals) Solids 19
1.2.2.2 Ionic Solids 19
1.2.2.3 Covalent Solids 20
1.2.2.4 Metallic Solids 21
1.2.2.5 Crystalline and Amorphous Solids 22
1.2.3 The Band Theory of Solids 27
1.2.3.1 Free Electron Gas Model 28
1.2.3.2 Nearly Free Electron Gas Model and Period Structures 29
1.2.3.3 Electron Bands and Gaps: The Origin of Band Gap in Solids 33
1.2.3.4 Metals, Semiconductors and Insulators 35
1.3 Thermodynamics of Materials 36
1.3.1 Nucleation and Growth of Solids 37
1.4 Kinetics of Materials 41
1.5 Nanostructures and Bulk Nanostructured Materials 43
1.5.1 Dimensionality in Nanomaterials 44
1.5.2 Two-Dimensional (2D) Nanostructures 46
1.5.2.1 Quantum Wells or Nanofilms: Dimensionality Effect 48
1.5.3 One-Dimensional Nanostructures (Quantum Wires or Tubes) 50
1.5.3.1 Quantum Wires: Dimensionality Effect 51
1.5.4 Zero-Dimensional Nanostructures 52
1.5.4.1 Quantum Dots or Nanoparticles: Dimensionality 52
1.5.5 Bulk Nanostructured Materials 52
References 54
2 An Overview to Electrochemistry 55
Abstract 55
2.1 Introduction to Electrochemistry in Materials Science 55
2.2 Principles of Electrochemistry 56
2.3 Equilibrium Electrochemistry 56
2.3.1 Ions: Formation, Thermodynamics and Interactions 56
2.3.2 Electrochemical Cells 61
2.4 Ion Transport 62
2.4.1 Migration 62
2.4.2 Diffusion of Ions 65
2.5 Dynamic Electrochemistry: Processes at Electrodes 66
2.5.1 The Electrode Double Layer 67
2.5.2 Zeta Potential ({/varvec /zeta}) 69
2.5.3 Electrode Potentials 71
2.5.4 The Rate of Charge Transfer: Electrode Kinetics and the Butler-Volmer Equation 73
2.5.5 Polarisation 77
2.6 Electrochemical Instrumentation and Techniques 78
2.6.1 Electrochemical Cell 78
2.6.2 Electrochemical Tests and Techniques 80
References 85
3 Fundamentals and Principles of Electrode-Position 86
Abstract 86
3.1 Introduction 86
3.2 Electrolysis 87
3.2.1 Electrolysis Cell 87
3.2.2 Electrodeposition Cells and Reactions 88
3.2.3 Electrodeposition Electrolytes 89
3.2.3.1 Aqueous Electrodeposition Electrolytes 89
3.2.3.2 Ionic Electrodeposition Electrolytes 91
3.2.4 Electrodeposition Techniques and Classification 92
3.2.5 Electrodeposition Kinetics: Potential-Current Relationship 92
3.2.5.1 Activation or Charge Transfer Controlled Electrodeposition 93
3.2.5.2 Mass Transport or Diffusion Controlled Electrodeposition 94
3.2.6 Co-electrodeposition of Various Ions 96
3.2.6.1 Electrodeposition of Alloys 98
3.2.6.2 Hydrogen Evolution: Mechanism and Overpotential 99
3.2.6.3 Current Efficiency 100
3.3 Nucleation and Growth of Electrodeposits 101
3.3.1 Atomistic View 101
3.3.2 Thermodynamics of Nucleation 102
3.3.3 Kinetics of Electrocrystallisation 104
3.3.4 Surface Morphology and Roughness 113
3.4 Characterisation of Initial Stages of Electrodeposition Process 118
3.4.1 Scanning Probe Microscopy (SPM) Techniques 118
3.4.1.1 Electrochemical Scanning Tunneling Microscopy (EC-STM) 118
3.4.1.2 Scanning Electrochemical Potential Microscopy (SECPM) 120
3.4.1.3 Scanning Electrochemical Microscopy (SECM) 120
3.4.1.4 Electrochemical Atomic Force Microscopy 121
3.4.2 Electrochemical Quartz Crystal Microbalance (EQCM) 122
3.4.3 Oblique Incidence Reflectivity Difference 124
3.5 Modified Electrodeposition Processes Under External Forces 125
3.5.1 Magnetic Electrodeposition 125
3.5.2 Sono-Electrodeposition 127
References 129
4 Electrodeposition of 2D and 3D Meso and Nanostructures 133
Abstract 133
4.1 Introduction 133
4.2 UPD and OPD: General Consideration 134
4.2.1 Underpotential Deposition (UPD) 135
4.2.2 UPD and OPD in Electrodeposited Lead (Pb) on Copper (Cu) 136
4.2.3 UPD and OPD in Electrodeposited Lead (Pb) on Gold (Cu) 144
4.3 Three Dimensional (3D) Growth of Electrodeposits 149
4.3.1 3D Nuclei as Free Standing Meso- and Nano-Structures 150
4.3.1.1 3D Mesoparticles, Nanoparticles and Nanowires 150
Electrodeposition of Nickel Nanowires 151
Electrodeposition of Nickel Nanoparticles 152
4.3.1.2 3D Faceted Mesocrystals 153
Electrodeposition of Silver Mesocrystals 154
Electrodeposition of Copper Mesocrystals 160
Electrodeposition of Other Metal Mesocrystals 163
4.3.2 Multiple 3D Nuclei and Coalescence for Film Growth 168
4.3.2.1 Electrodeposition of Nickel on Copper 168
4.3.2.2 Electrodeposition of Nickel on Silicon (3D Nucleation and Coalescence for Film Growth) 172
Electrodeposition of Nickel from Dilute Sulfate Solution on Silicon 173
The Effects of Nickel Content, Chloride Ions and PH 175
Microstructure of Electrodeposited Nickel Films on n-Si(111): Transition from Particle to Continuous Film 180
Island Growth for Tuning Magnetisation Mode: Transition from Particle to Continuous Film 182
4.3.2.3 Electrodeposition of Nickel on HOPG 185
4.3.3 3D Faceted Core-Shell Mesocrystals 188
4.3.4 Hexagonal and Polyhedral Ag Core-Ni Shell Mesocrystals 188
4.3.5 Truncated Icosahedral and Pyramidal Ag Core-Ni Shell Mesocrystals 191
References 193
5 Template Electrodeposition of Nanowires Arrays 196
Abstract 196
5.1 Introduction 196
5.2 Template 197
5.2.1 Track-Etched Templates 197
5.2.2 Anodic Aluminum Oxide (AAO) Templates 199
5.2.2.1 Current-Transients Achieved by Multi-step Anodic Oxidation of Aluminum 200
5.2.2.2 Self-organization Mechanism of Nanopores 202
5.2.2.3 Enhancement of Ordering Degree of AAO Templates by Three-Step Anodic Oxidation 205
5.2.2.4 Effect of Voltage and Electrolyte on Pore Diameter of AAO Templates 207
5.2.2.5 Topography and Kinetic Roughening of AAO Templates 208
5.3 Electrodeposition into Template 214
5.3.1 Template Electrodeposition: Electrochemical Consideration 215
5.3.1.1 General Mechanism 215
5.3.1.2 Electrochemical Implications 216
5.3.2 Template Electrodeposition: Techniques 218
5.3.2.1 Direct Current Template Electrodeposition 218
5.3.2.2 Alternating Current Template Electrodeposition 219
5.3.2.3 Pulse Current Template Electrodeposition 223
5.4 Magnetic Nanowires 224
5.4.1 Regular Metal and Alloy Magnetic Nanowires 225
5.4.1.1 Nickel Nanowires 225
5.4.1.2 Cobalt Nanowires 231
5.4.1.3 Cobalt-Nickel Alloy Nanowires 234
5.4.2 Core-Shell Nanowire Arrays 241
5.4.2.1 Core-Shell Structure in Co-P Nanowires 241
5.4.2.2 Core-Shell TM@Au Nanowires 248
5.4.3 Multilayered Nanowires 249
5.4.3.1 Electrodeposition Techniques of Multilayered Nanowires 250
5.4.3.2 Electrodeposition Mechanism of Ni/Cu Multilayered Nanowires from Single Bath 251
5.4.3.3 Electrodeposition Mechanism of CoNiCu/Cu Multilayered Nanowires from Single Bath 254
5.4.3.4 GMR and Magnetism in Electrodeposited Multilayered Nanowires 257
5.4.4 Diameter Modulated Nanowires 262
References 263
6 Electrodeposited Nanocrystalline Films and Coatings 269
Abstract 269
6.1 Introduction 269
6.2 Electrodeposition of Nanocrystalline Films 269
6.3 Pulse Electrodeposition 270
6.3.1 Electrochemical Implications of Pulse Current Technique 270
6.3.2 Principles of Pulse Electrodeposition 272
6.3.3 Electrochemical Aspects of Pulse Electrodeposition 274
6.3.4 Pulse Electrodeposition Conditions for Nanocrystalline Films 279
6.4 Electrodeposited Nanocrystalline Nickel Films 280
6.4.1 Surface Morphology and Roughness of Nanocrystalline Ni Films 282
6.4.2 Crystallite Size and Crystallographic Texture 285
6.4.3 Microhardness of Nanocrystalline Nickel Films 289
6.4.4 Magnetic Properties of Nanocrystalline Nickel Films 289
6.4.5 Corrosion Behaviour of Nanocrystalline Nickel Films 291
6.4.5.1 Electrochemical Corrosion Studies in NaOH Solution 292
6.4.5.2 Electrochemical Corrosion Studies in H2SO4 Solution 294
References 295
7 Electrodeposited Nanocomposite Films 297
Abstract 297
7.1 Introduction 297
7.2 Principles of Electrodeposition of Nanocomposites 298
7.2.1 Electrochemical Aspects of Co-electrodeposition of Nanocomposites 298
7.2.2 Models 298
7.3 Effective Factors in Co-electrodeposition of Nanocomposites 302
7.3.1 Electrodeposition Control Technique 302
7.3.1.1 Direct Current Electrodeposition: Effect of Current Density 302
7.3.1.2 Pulse Electrodeposition 305
7.3.2 Particle Properties 306
7.3.3 Electrolyte Parameters 307
7.3.3.1 Agglomeration Control 307
7.3.3.2 Surfactants 308
7.3.3.3 Particle Concentration 308
7.3.3.4 Electrolyte Agitation 311
7.3.3.5 Electrolyte Temperature 312
7.4 Properties of Nanocomposite Coatings 312
7.4.1 Mechanical Properties of Ni-CNT Nanocomposite Films 312
7.4.2 Corrosion Behavior of Ni-MWCNT Coatings in 3.5% NaCl 314
References 317
8 Miscellaneous Electrodeposited Nanostructures 319
Abstract 319
8.1 Scanning-Tunneling Assisted Electrodeposition of Nanostructures 319
8.2 Lithographically Patterned Nanowire Electrodeposition 322
8.3 Electrodeposited Mesoporous Nanostructures by Lyotropic Liquid Crystals 323
8.4 Nanostructures by Galvanic Displacement 324
References 326
Index 327