Schmuki / Virtanen Electrochemistry at the Nanoscale

1. Auflage 2009
ISBN: 978-0-387-73582-5
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 471 Seiten

For centuries, electrochemistry has played a key role in technologically important areas such as electroplating or corrosion. In recent decades, electrochemical methods are receiving increasing attention in important strongly growing fields of science and technology such as nanosciences (nanoelectrochemistry) and life-sciences (organic and biological electrochemistry).

Characterization, modification and understanding of various electrochemical interfaces or electrochemical processes at the nanoscale, has led to a huge increase of the scientific interest in electrochemical mechanisms as well as of application of electrochemical methods in novel technologies. This book presents exciting emerging scientific and technological aspects of the introduction of the nanodimension in electrochemical approaches are presented in 12 chapters/subchapters.

Autoren/Hrsg.

Schmuki, Patrik

Virtanen, Sannakaisa

Inhaltsverzeichnis

1;Nanostructure Science and Technology;2
2;Preface;5
3;Contents;7
4;Contributors;9
5;Theories and Simulations for Electrochemical Nanostructures;11
5.1;1.1 Introduction;11
5.2;1.2 Simulations of Electrochemical Nanostructures;12
5.2.1;2.1 Computer Simulation Techniques for Nanostructures;13
5.2.2;2.2 Interaction Potentials;16
5.2.3;2.3 The Creation of Atomic Clusters with the Aid of an STM Tip;17
5.2.4;2.4 The Filling of Nanoholes;24
5.3;1.3 Electron Transfer Through Functionalized Adsorbates and Films;27
5.3.1;3.1 Electron Exchange with a Monolayer;27
5.3.2;3.2 Metal--Adsorbate-Metal Systems;28
5.3.2.1;3.2.1 Two-Step Mechanism;29
5.3.2.2;3.2.2 Resonant Transition;30
5.3.2.3;3.2.3 Adiabatic Limit;34
5.3.3;3.3 Two Intermediate States;36
5.3.3.1;3.3.1 Electron Exchange via Two Bridge States;37
5.3.3.2;3.3.2 Electron Exchange via Two Equal Reactants;37
5.4;1.4 Conclusion;40
6;SPM Techniques;42
6.1;2.5 Introduction;42
6.2;2.6 Electrochemical STM;44
6.2.1;2.1 Principle of Operation and Experimental Considerations;45
6.2.2;2.2 High-Resolution In Situ Studies of Electrode Surface Structure ;47
6.2.3;2.3 Studies of Phase Transitions and Transport on Electrode Surfaces;54
6.2.4;2.4 Studies of Electrochemical Phase Formation Processes;60
6.2.5;2.5 Scanning Tunneling Spectroscopy;66
6.3;2.7 Electrochemical AFM;69
6.3.1;3.1 Experimental Realization and Operation Modes;70
6.3.2;3.2 In Situ AFM Imaging of Electrode Surfaces;72
6.3.3;3.3 Forces at Electrochemical Interfaces;75
6.4;2.8 Other SPM Techniques;76
6.5;2.9 Nanostructuring by Electrochemical SPM;77
6.5.1;5.1 Nanostructuring by Local Mechanical Interactions;77
6.5.2;5.2 Nanostructuring by Modification of the Local Electrochemistry;79
6.5.3;5.3 Nanostructuring by Electrochemical Nanocells;80
6.6;2.10 Conclusions;82
7;X-ray Lithography Techniques, LIGA-Based Microsystem Manufacturing: The Electrochemistry of Through-Mold Deposition and Material Properties;88
7.1;3.11 Introduction to LIGA Fabrication and Its Applications;88
7.1.1;1.1 LIGA Process Flow;90
7.1.2;1.2 LIGA History;95
7.1.3;1.3 LIGA Applications;98
7.2;3.12 Electrodeposition into Deep High-Aspect-Ratio Features for LIGA;101
7.2.1;2.1 Introduction;102
7.2.2;2.2 Workpiece- and Pattern-Scale Effects;104
7.2.3;2.3 The Feature Scale;105
7.3;3.13 Summary: Uniformity at the Workpiece, Pattern, and Feature Scales in LIGA;113
7.4;3.14 Electrodeposition in LIGA: Materials and Other Aspects;114
7.5;3.15 Properties and Structure of Electrodeposited Materials for LIGA-Based Microsystem Applications;116
7.5.1;5.1 Introduction;116
7.5.2;5.2 Measurement Techniques for Strength and Ductility;117
7.5.3;5.3 Grain Refinement for Improved Electrodeposit Strength;119
7.5.4;5.4 Particulate Additive Effects;133
7.5.5;5.5 Modulus of Electrodeposits;134
7.5.6;5.6 Summary: Electrodeposited Materials for LIGA-Based Microsystems;138
7.6;3.16 Other Aspects of LIGA Technology;139
8;Direct Writing Techniques: Electron Beam and Focused Ion Beam;148
8.1;4.17 Introduction;148
8.2;4.18 Theoretical Aspects;149
8.2.1;2.1 Generality;149
8.2.2;2.2 Interaction of Energetic Particles with Solids;149
8.2.3;2.3 Scattering of Particles;150
8.2.4;2.4 Stopping of Particles in Solids;154
8.2.5;2.5 Radiation Damage in Solids;158
8.2.6;2.6 Sputtering;160
8.3;4.19 Micro- and Nanostructuring by Electron-Beam Approaches and Electrochemical Reactions;161
8.3.1;3.1 Microstructuring by Conventional EBL and Electrochemical Reactions;161
8.3.1.1;3.1.1 Basics on Electron-Beam Lithography;161
8.3.1.2;3.1.2 Nanostructuring by EBL and Electroplating;164
8.3.1.3;3.1.3 Nanostructuring by EBL and Electrochemical Etching;165
8.3.2;3.2 Electrochemical Micropatterning Using E-beam Modification of SAMs;166
8.3.2.1;3.2.1 Self-Assembled Monolayers (SAMs);166
8.3.2.2;3.2.2 Selective Electrodeposition Using E-beam-induced Modification of SAMs;168
8.3.3;3.3 Micro- and Nanostructuring by EBICD and Electrochemical Reactions;169
8.3.3.1;3.3.1 E-beam-Induced Deposition (EBID) Technique;169
8.3.3.2;3.3.2 EBICD Technique;170
8.3.3.3;3.3.3 Contamination Lithography;172
8.3.3.4;3.3.4 Micro- and Nanostructuring by EBICD Technique and Electrodeposition;172
8.3.3.5;3.3.5 Microstructuring by EBICD Technique and Electrochemical Etching;174
8.4;4.20 Material Processing by FIB;178
8.4.1;4.1 Generation of Focused Ion Beams;180
8.4.2;4.2 Ion Optics;181
8.4.3;4.3 Material Processing by Focused Ion Beams;182
8.4.4;4.4 Microstructuring by FIB and Electrochemical Reactions;182
9;Wet Chemical Approaches for Chemical Functionalization of Semiconductor Nanostructures;191
9.1;5.21 Introduction;191
9.2;5.22 Porous Silicon;192
9.2.1;2.1 Preparation of Porous Silicon;193
9.2.2;2.2 Reactive Surface Species on PSi Surfaces;194
9.2.2.1;2.2.1 Hydrogen Termination;194
9.2.2.2;2.2.2 Deuterium Termination;196
9.2.2.3;2.2.3 Halide Termination;196
9.2.3;2.3 Chemical Derivatization of PSi Surfaces Through Si--C;197
9.2.3.1;2.3.1 Metal-Induced Hydrosilylation;197
9.2.3.2;2.3.2 Photochemical Hydrosilylation;201
9.2.3.3;2.3.3 Thermal Hydrosilylation;205
9.2.3.4;2.3.4 Microwave-Irradiation-Induced Hydrosilylation;210
9.2.3.5;2.3.5 Hydrosilylation of Alkenes and Alkynes Initiated by Hydride Abstraction;212
9.2.3.6;2.3.6 Reaction with Grignard and Alkyl Lithium Reagents;213
9.2.3.7;2.3.7 Reaction with Alkyl Halides under Microwave Irradiation;215
9.2.3.8;2.3.8 Electrochemical Functionalization;217
9.2.4;2.4 Chemical Derivatization of PSi Surfaces Through Si--O--C;224
9.2.4.1;2.4.1 Electrochemical Methoxylation;224
9.2.4.2;2.4.2 Photoderivatization with Carboxylic Acids;225
9.2.4.3;2.4.3 Thermal Reaction of H-Terminated PSi with Alcohols;227
9.2.4.4;2.4.4 Thermal Reaction of Halogenated PSi with Alcohols;229
9.2.4.5;2.4.5 Thermal Hydrosilylation of Aldehydes;229
9.2.4.6;2.4.6 Reaction with Benzoquinone;231
9.2.5;2.5 Miscellaneous;232
9.2.5.1;2.5.1 Formation of Organic Layers through Si--Si Bonds;232
9.2.5.2;2.5.2 Plasma Modification;232
9.2.6;2.6 Preparation of Polymer/PSi Hybrids;233
9.2.7;2.7 Covalent Immobilization of Biomolecules;234
9.2.8;2.8 Applications;235
9.2.8.1;2.8.1 Surface Passivation;235
9.2.8.2;2.8.2 Electroluminescence Stabilization;236
9.2.8.3;2.8.3 Desorption/Ionization on Silicon (DIOS);238
9.2.8.4;2.8.4 Sensing;238
9.3;5.23 Porous-Based Germanium Materials;241
9.3.1;3.1 Formation;241
9.3.1.1;3.1.1 Porous Germanium;241
9.3.1.2;3.1.2 Macroporous Germanium;246
9.3.1.3;3.1.3 PSi--Germanium;248
9.3.1.4;3.1.4 Chemical Functionalization of Hydride-Terminated Porous Germanium;248
9.4;5.24 Conclusions and Perspectives;249
10;The Electrochemistry of Porous Semiconductors;257
10.1;6.25 Introduction;257
10.2;6.26 Charging of Porous Electrodes;258
10.2.1;2.1 Accumulation;258
10.2.2;2.2 Depletion;261
10.3;6.27 Electrochemical Reactions;263
10.3.1;3.1 Minority-Carrier Reactions;265
10.3.1.1;3.1.1 Electron Tunneling;265
10.3.1.2;3.1.2 Photogeneration;268
10.3.1.3;3.1.3 Minority-Carrier Injection;276
10.3.2;3.2 Majority-Carrier Reactions;277
10.3.2.1;3.2.1 p-Type Semiconductors;277
10.3.2.2;3.2.2 n-Type Semiconductors;278
10.3.3;3.3 Combined Majority/Minority-Carrier Processes;279
10.3.3.1;3.3.1 Hole Injection;279
10.3.3.2;3.3.2 Electron Injection;280
10.4;6.28 Conclusion;283
11;Deposition into Templates;287
11.1;7.29 Introduction;287
11.2;7.30 Templates Used;288
11.2.1;2.1 Track-Etch Membranes;288
11.2.2;2.2 Alumina Membranes;290
11.2.3;2.3 Colloidal Crystals;293
11.3;7.31 Template-Synthesis Strategies;295
11.3.1;3.1 Electrochemical Deposition;295
11.3.1.1;3.1.1 Electrodeposition of Metals;295
11.3.1.2;3.1.2 Electrodeposition of Polymers;297
11.3.2;3.2 Electroless Deposition;297
11.3.3;3.3 Sol--gel Deposition;301
11.3.4;3.4 Chemical Vapor Deposition;302
11.3.5;3.5 Atomic Layer Deposition;303
11.4;7.32 Applications in Nanoelectrochemistry;304
11.4.1;4.1 Gold Nanoelectrodes;306
11.4.1.1;4.1.1 Fabrication;306
11.4.1.2;4.1.2 Current Response of the NEE;306
11.4.1.3;4.1.3 Detection Limits;307
11.4.1.4;4.1.4 Supporting Electrolyte Effect;309
11.4.2;4.2 Carbon Nanoelectrodes;309
11.4.2.1;4.2.1 Fabrication;311
11.4.2.2;4.2.2 Measuring EOF in CNM;311
11.4.2.3;4.2.3 Redox Control of EOF;314
11.4.3;4.3 Li-ion Battery Nanoelectrodes;315
11.4.3.1;4.3.1 Fabrication;317
11.4.3.2;4.3.2 Measuring Rate Capabilities;318
11.4.3.3;4.3.3 Other Electrochemical Studies;319
11.4.3.4;4.3.4 Nanosphere-Templated Structures;320
11.4.4;4.4 Ion Channels;320
11.4.4.1;4.4.1 Electrochemical Measurements;321
11.4.5;4.5 DNA Ion Channels;322
11.5;7.33 Conclusion;324
12;Electroless Fabrication of Nanostructures;329
12.1;8.34 Fundamental (with Contributions from A. Sugiyama);329
12.2;8.35 Superfilling of Cu into Patterned Substrates by Electroless Plating (with Contributions from J. Sasano);331
12.2.1;2.1 Introduction;331
12.2.2;2.2 Superfilling by Electrodeposition;331
12.2.3;2.3 Superfilling by Electroless Deposition;332
12.2.4;2.4 Summary;336
12.3;8.36 A Novel Process for Fabrication of ULSI Interconnects (with Contributions from M. Yoshino);337
12.3.1;3.1 Introduction;337
12.3.2;3.2 Thermal Stability of Electroless Ni-Alloy Diffusion Barrier Layer;338
12.3.3;3.3 Fabrication of Barrier Layer on SiO 2 Substrate Without Sputtered Seed Layer;340
12.3.4;3.4 All-Wet Fabrication of Cu Wiring;341
12.4;8.37 Magnetic Nanodot Arrays for Patterned Media (with Contributions from J. Kawaji);342
12.4.1;4.1 Introduction;342
12.4.2;4.2 Fabrication of Magnetic Nanodot Arrays on Si Wafer;343
12.4.3;4.3 Magnetic Properties of CoNiP Nanodot Arrays;344
12.5;8.38 Nanoparticles;346
12.5.1;5.1 Oxide Nanoparticles (with Contributions from T. Nakanishi);346
12.5.2;5.2 Metallic Mesoporous Particles (with Contributions from T. Momma);349
13;Electrochemical Fabrication of Nanostructured, Compositionally Modulated Metal Multilayers (CMMMs);356
13.1;9.39 Introduction;356
13.2;9.40 Experimental Apparatus and Schemes;357
13.2.1;2.1 Dual-Bath Electrodeposition;358
13.2.2;2.2 Single-Bath Electrodeposition;360
13.2.3;2.3 Electrodeposition by Flow Modulation;365
13.3;9.41 Issues Related to Electrodeposition of Nanostructured Metal Multilayers;366
13.3.1;3.1 Estimation of Layer Thickness and Composition;366
13.3.2;3.2 Effect of Displacement Reaction;368
13.3.3;3.3 Interfacial and Phase Instability;370
13.4;9.42 Optimization of Electrodeposition Processes;372
13.4.1;4.1 Electrolyte Stability and Electrochemical Cells;373
13.4.2;4.2 Control of Electrochemical Parameters;375
13.4.3;4.3 Control of Interface Structure and Properties;376
13.5;9.43 Other Compositionally Modulated Systems: Ceramics and Seminconductors;377
13.6;9.44 Summary;379
14;Corrosion at the Nanoscale;384
14.1;10.45 Introduction;384
14.2;10.46 Corrosion and Protection of Materials for the Nanoelectronics: The Case of Copper;385
14.2.1;2.1 Active Dissolution;385
14.2.2;2.2 Protection by Corrosion Inhibitors;388
14.2.3;2.3 Passivation;391
14.3;10.47 Nanostructure of Passive Films;396
14.4;10.48 Nanostructural Aspects of Passivity Breakdown and Localized Corrosion;401
14.4.1;4.1 Dissolution in the Passive State and Passivity Breakdown;401
14.4.2;4.2 Initiation of Pitting Corrosion;405
14.4.3;4.3 Tip-Induced Controlled Localized Corrosion;408
14.5;10.49 Conclusion;410
15;Nanobioelectrochemistry;414
15.1;11.50 Overview;414
15.2;11.51 Electrochemistry of Biomolecules at the Nanoscale;416
15.3;11.52 Electrochemistry of Self-Assembled Nanostructured Biomolecules;419
15.4;11.53 Electrochemistry and AFM of Nanoscale DNA Surface Layers on Conducting Surfaces;422
15.5;11.54 Nanoscale Electrochemical Biosensor Devices;430
15.5.1;5.1 Template-Synthesized Biomolecule Nanotubes;431
15.5.2;5.2 Nanoparticle Magnetic Control of Bioelectrocatalytic Processes;435
15.5.3;5.3 Detection Limits for Nanoscale Biosensors;437
15.6;11.55 Conclusions;437
16;Self-Organized Oxide Nanotube Layers on Titanium and Other Transition Metals;441
16.1;12.56 Introduction;441
16.2;12.57 Overview on the Electrochemistry of Valve Metals;443
16.3;12.58 Formation of Nanotubular Layers;445
16.3.1;3.1 I--U Curves;445
16.3.2;3.2 I-t Curves and Initiation of Porous Layers;447
16.3.2.1;3.2.1 Current Oscillations;448
16.3.3;3.3 Steady-State Growth;449
16.4;12.59 Factors Affecting Tube Morphology;449
16.4.1;4.1 pH of the Electrolyte;449
16.4.2;4.2 Effect of Anodization Voltage;451
16.4.3;4.3 Effect of Viscosity;452
16.4.4;4.4 Effect of Water Content;453
16.4.5;4.5 Formation of Multilayers and Free-Standing Membranes;454
16.4.6;4.6 Different Metal Substrates;454
16.5;12.60 Structure and Chemistry;457
16.5.1;5.1 Crystallographic Structure;457
16.5.2;5.2 Chemical Composition;459
16.6;12.61 Properties of the Tubes;459
16.6.1;6.1 Photoresponse of the Tubes;460
16.6.2;6.2 Doping, Dye Sensitization;461
16.6.3;6.3 Insertion Properties for Li and H + and Strong Electrochromic Effects;462
16.6.4;6.4 Photocatalysis;463
16.6.5;6.5 Highly Adjustable Wetting Properties;464
16.6.6;6.6 Biomedical Applications;464
16.6.7;6.7 Other Aspects;467
17;Index;473