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Electrocrystallization in Nanotechnology. Edited by Georgi StaikovCopyright 8 2007 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-31515-4

Contents

Preface xi

List of Contributors xiii

I Fundamentals

1 The Impact of Electrocrystallization on Nanotechnology 3

Georgi Staikov and Alexander Milchev

1.1 Introduction 3

1.2 Thermodynamic Properties of Large and Small Phases 4

1.2.1 The State of Thermodynamic Equilibrium 4

1.2.2 Electrochemical Supersaturation and Undersaturation 6

1.2.3 The Thermodynamic Work for Nucleus Formation 7

1.2.3.1 Classical Nucleation Theory 81.2.3.2 Atomistic Nucleation Theory 9

1.3 Kinetics of Nucleus Formation in Electrocrystallization 10

1.4 Energy State of the Electrode Surface and Spatial Distribution of

Nanoclusters 11

1.5 Electrochemical Growth of Nanoparticles and Ultrathin Films 14

1.5.1 Growth of 3D Nanoclusters 15

1.5.2 Growth of 2D Nanoclusters and Formation of UPD Monolayers 17

1.6 Localization of Electrocrystallization Processes and Nanostructuring 20

1.7 Conclusion 24

Acknowledgments 25References 25

2 Computer Simulations of Electrochemical Low-dimensional Metal Phase

Formation 30

Marcelo M. Mariscal and Ezequiel P. M. Leiva

2.1 Introduction 30

2.2 Molecular Dynamics Simulations 32

2.2.1 Generalities 32

2.2.2 Nanostructuring of Metallic Surfaces 33

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2.3 Monte Carlo Method 37


2.3.2 Off-lattice Models 40

2.3.2.1 Stability of Metallic Nanostructures 40

2.3.3 Lattice Models 44

2.3.3.1 Introduction 442.3.3.2 Electrocrystallization 46

2.3.3.3 Dynamics of Crystal Growth 51

2.3.3.4 Simulation of a Complex Underpotential Deposition System 53

2.4 Brownian and Langevin Dynamics Simulations 54


2.4.2 Applications in Electrochemical Nanostructuring and Crystal

Growth 55

2.5 Conclusions and Outlook 58

Acknowledgments 59

References 59

3 Electrodeposition of Metals in Templates and STM Tip-generated 0D

Nanocavities 61

Wolfgang Kautek

3.1 Introduction 61

3.2 Bottom-up Template Approach 61

3.3 Top-down SPM Approach 66

3.4 Thermodynamics of Low-dimensional Phases 68

3.5 Experiments on the Electrodeposition in STM-tip-generated

Nanocavities 693.6 Underpotential Behavior of Bismuth on Gold 70

3.7 Zero-dimensional Bi Deposition 72

3.8 Conclusions 74

Acknowledgment 75

References 75

4 Nanoscale Electrocrystallization of Metals and Semiconductors from Ionic

Liquids 79

Walter Freyland, Chitradurga L. Aravinda, and Ditimar Borissov

4.1 Introduction 794.2 Some Electrochemical and Interfacial Characteristics of Ionic Liquids

(ILs) 80

4.3 Variable Temperature Electrochemical SPM Technique for Studies with

Ionic Liquids 81

4.4 Underpotential Deposition of Metals: Phase Formation and

Transitions 82

4.4.1 Ag on Au(111): Aqueous versus Ionic Liquid Electrolytes 83

4.4.2 Zn on Au(111): Spinodal Decomposition and Surface Alloying 86

4.5 Overpotential Deposition of Metals, Alloys and Semiconductors 89

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4.5.1 CoaAl, NiaAl and TiaAl Alloy Deposition 89

4.5.2 Nanoscale Growth of AlaSb Compound Semiconductors 92

4.6 Concluding Remarks 93

Acknowledgment 94

References 94

5 Superconformal Film Growth 96

Thomas P. Moffat, Daniel Wheeler, and Daniel Josell

5.1 Introduction 96

5.2 Competitive Adsorption: Inhibition versus Acceleration 98

5.3 Quantifying the Impact of Competitive Adsorption on Metal Deposition

Kinetics 101

5.4 Feature Filling 104

5.5 Shape Change Simulations 107

5.6 Stability Analysis 110

5.7 Conclusions and Outlook 112References 113

II Preparation and Properties of Nanostructures

6 Localized Electrocrystallization of Metals by STM Tip Nanoelectrodes 117

Werner Schindler and Philipp Hugelmann

6.1 Electrochemistry in Nanoscale Dimensions 117

6.2 Jump-to-Contact Metal Deposition 118

6.3 Scanning Electrochemical Microscope 120

6.4 STM Tip Electrochemical Nanoelectrodes 1206.5 Metal Deposition by STM Tip Electrochemical Nanoelectrodes 122

6.6 Metal Dissolution by STM Tip Electrochemical Nanoelectrodes 124

6.7 The Importance of Nanoelectrode Tip Shape and Surface Quality 127

6.8 Localized Electrodeposition of Single Metal Nanostructures 129

6.9 Summary and Outlook 134

Acknowledgments 136

References 136

7 Fabrication of Ordered Anodic Nanoporous Alumina Layers and their

Application to Nanotechnology 138Hidetaka Asoh and Sachiko Ono

7.1 Introduction 138

7.2 Self-ordered Anodic Porous Alumina 139

7.2.1 Introduction 139

7.2.2 Controlling Factor of Self-ordering of Pore Arrangement in Anodic

Porous Alumina 140

7.2.3 Typical CurrentTime Transients at Constant Voltages 141

7.2.4 Change in the Porosity of Anodic Alumina with Increasing Formation

Voltage 142

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7.2.5 Typical Self-ordering Behavior 144

7.2.6 High-current-density/High-electric-field Anodization 145

7.2.7 New Self-ordering Conditions 147

7.3 Ideally Ordered Anodic Porous Alumina 148

7.3.1 Two-step Anodization 148

7.3.2 Fabrication of Ideally Ordered Anodic Porous Alumina 1507.3.3 Square Cell Arrangement 150

7.3.4 Detailed Observation of Square Cells 152

7.4 Anodic Porous Alumina with 3D Periodicity 154

7.4.1 Modulation of Channel Structure 154

7.4.2 2D/3D Composite Porous Alumina 154

7.5 Application of Nanoporous Alumina to a Mask for Fabrication of

Nanostructures 156

7.5.1 Nanopatterning: Conventional Lithography vs. Natural Lithography 156

7.5.2 Anodization of Al on a Si Substrate 157

7.5.3 Natural Lithography of Si Surfaces Using Anodic Porous Alumina as aMask 160

7.6 Summary 161

Acknowledgments 162

References 162

8 Electrochemical Fabrication of Metal Nanocontacts and Nanogaps 167

Fang Chen and N. J. Tao


8.2 Electrochemical Fabrication of Metal Nanocontacts 168

8.2.1 STM/AFM Assisted Method 1698.2.2 Electrodeposition on Surface-supported Electrodes 170

8.2.3 Self-terminated Method 172

8.2.4 Electrochemical Etching 173

8.2.5 Nanocontacts Prepared Using Nanopores 174

8.2.6 Solid State Electrochemical Reaction 174

8.2.7 Properties of Metal Nanocontacts 175

8.2.7.1 Mechanical Properties 175

8.2.7.2 Electron Transport 177

8.2.7.3 Electrochemical Properties 178

8.2.7.4 Device Properties 1808.2.7.5 Magnetic Properties 181

8.2.7.6 Sensing Properties 182

8.3 Electrochemical Fabrication of Metal Nanogaps 183

8.3.1 AC-loop Monitoring System 185

8.3.2 DC-loop Monitoring System 186

8.3.3 Electric Double Layer as Feedback 187

8.3.4 High-frequency Impedance as Feedback 188

8.3.5 Application of Nanogaps 188

8.4 Summary 190

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Acknowledgment 191

References 191

9 Nanowires by Electrochemical Step Edge Decoration (ESED) 195

Reginald M. Penner

9.1 Introduction 1959.2 General Considerations 196

9.3 Direct Nanowire Electrodeposition 198

9.4 Compound Nanowires by Cyclic Electrodeposition/Stripping 200

9.5 Electrochemical/Chemical Synthesis of Nanowires 202

9.6 Nanowire Thinning by Electrooxidation 204

9.7 Summary 206

Acknowledgments 206

References 206

10 Electrochemical Fabrication of Arrayed Nanostructures 208Takayuki Homma


10.2 Formation of Metal Nanodots Along the Step Edge of the Si(111)

Surface 208

10.3 Maskless Fabrication of Metal Nanodot Arrays using Electroless

Deposition Induced by Controlled Local Surface Activities 210

10.4 Conclusion 215

References 216

11 Electrodeposition of Two-dimensional Magnetic Nanostructures on SingleCrystal Electrode Surfaces 217

Philippe Allongue and Fouad Maroun


11.2 Ultrathin Magnetic Films 219

11.2.1 Magnetic Moment of Ultrathin Films 220

11.2.2 In Situ Magnetic Characterizations 223

11.2.2.1 Alternating Gradient Field Magnetometry (AGFM) 224

11.2.2.2 Magneto Optical Kerr Effect (MOKE) 225

11.2.3 Description and Exploitation ofin SituMagnetic Measurements 225

11.3 Electrochemical Growth and Magnetic Properties of Iron Group Films onAu(111) 227

11.3.1 Electrochemistry of Au(111) in Iron Group Metal Solutions 227

11.3.2 Ni/Au(111) 228

11.3.2.1 Morphology and Structure 228

11.3.2.2 Magnetic Properties 229

11.3.3 Co/Au(111) 230



11.3.4 Fe/Au(111) 235

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11.4 Concluding Remarks 238

Acknowledgments 239

References 239

12 Electrodeposition and Properties of Nanoscale Magnetic/Non-magnetic

Metallic Multilayer Films 242

Laszlo Peter and Imre Bakonyi


12.2 Electrodeposition 243

12.2.1 Electrolyte Composition 243

12.2.2 Deposition Conditions of the More Noble Layer 246

12.2.3 Deposition of the Less Noble Layer 247

12.2.4 Various Multilayer Deposition Modes 249

12.2.5 Nucleation of the Layers on Each Other 24912.3 Properties 250

12.3.1 Structure 250

12.3.2 Magnetic Properties 253

12.3.3 Magnetoresistance 256

12.4 Summary 258

Acknowledgments 259

References 259

Index 261

X Contents

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