xiv
Contents
11.4.1 Lyotropic Systems Suitable for Templates
in Electrodeposition Processes . . . . . . . . . . . . . . . . . . . . . 400
11.4.2 Nanoporous Metals and Oxides Obtained
from the H 1 Phase of Lyotropic Liquid Crystals . . . . . . 403
11.4.3 Semiconductors Obtained with Hexagonal
Lyotropic Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
11.4.4 Electrodeposited Polymers by Using Various
Lyotropic Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
11.4.5 Dual Template Methods Involving Lyotropic
Liquid Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
11.4.6 Micelle Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
11.4.7 Self-assembled Monolayers (SAMs)
as Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
12 Localized or Spatially Selective Electrodeposition Methods . . . . . . . . 423
12.1 Electrodeposition in Ultrathin Solution Layers Along
the Edge of the Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
12.1.1 Transport and Fluid Motion in Thin-Layer Cells
of Various Orientations . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
12.1.2 Deposition of Metal-Based Structures Under
Cryogenic Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
12.1.3 Miscellaneous Deposits Obtained in Cryostatic
Thin-Layer Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
12.2 Two-Plate Thin-Layer Cells for Electron Microscopic
Studies of Electrodeposition Processes . . . . . . . . . . . . . . . . . . . . . . 432
12.2.1 Electrochemical Cells in High-Vacuum
Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
12.2.2 In Situ Electrochemical Nucleation Studies
with TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
12.2.3 In Situ Electroplating Studies with TEM . . . . . . . . . . . . 437
12.2.4 In Situ TEM Studies of Nanostructures Related
to Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
12.2.5 Chemical Changes in Thin-Layer Cells Induced
by the Electron Beam . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
12.3 Deposition at the Liquid–Liquid Interface . . . . . . . . . . . . . . . . . . . . 440
12.3.1 Basic Overview of the Appropriate Systems . . . . . . . . . 440
12.3.2 Particle Deposition at the Liquid–Liquid Interface . . . . 442
12.3.3 Electrodeposition of Various Films at the ITIES . . . . . . 446
12.3.4 Electrodeposition Near the Solid–Liquid–Liquid
Three-Phase Boundary . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
12.3.5 Tip- and Filament-Assisted Deposition
at the Liquid–Liquid Interface . . . . . . . . . . . . . . . . . . . . . 449
12.4 Deposition with the Help of Tips . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
12.4.1 Deposition of Microcolumns by Using Microtips . . . . . 453
Contents
11.4.1 Lyotropic Systems Suitable for Templates
in Electrodeposition Processes . . . . . . . . . . . . . . . . . . . . . 400
11.4.2 Nanoporous Metals and Oxides Obtained
from the H 1 Phase of Lyotropic Liquid Crystals . . . . . . 403
11.4.3 Semiconductors Obtained with Hexagonal
Lyotropic Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
11.4.4 Electrodeposited Polymers by Using Various
Lyotropic Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
11.4.5 Dual Template Methods Involving Lyotropic
Liquid Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
11.4.6 Micelle Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
11.4.7 Self-assembled Monolayers (SAMs)
as Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
12 Localized or Spatially Selective Electrodeposition Methods . . . . . . . . 423
12.1 Electrodeposition in Ultrathin Solution Layers Along
the Edge of the Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
12.1.1 Transport and Fluid Motion in Thin-Layer Cells
of Various Orientations . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
12.1.2 Deposition of Metal-Based Structures Under
Cryogenic Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
12.1.3 Miscellaneous Deposits Obtained in Cryostatic
Thin-Layer Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
12.2 Two-Plate Thin-Layer Cells for Electron Microscopic
Studies of Electrodeposition Processes . . . . . . . . . . . . . . . . . . . . . . 432
12.2.1 Electrochemical Cells in High-Vacuum
Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
12.2.2 In Situ Electrochemical Nucleation Studies
with TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
12.2.3 In Situ Electroplating Studies with TEM . . . . . . . . . . . . 437
12.2.4 In Situ TEM Studies of Nanostructures Related
to Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
12.2.5 Chemical Changes in Thin-Layer Cells Induced
by the Electron Beam . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
12.3 Deposition at the Liquid–Liquid Interface . . . . . . . . . . . . . . . . . . . . 440
12.3.1 Basic Overview of the Appropriate Systems . . . . . . . . . 440
12.3.2 Particle Deposition at the Liquid–Liquid Interface . . . . 442
12.3.3 Electrodeposition of Various Films at the ITIES . . . . . . 446
12.3.4 Electrodeposition Near the Solid–Liquid–Liquid
Three-Phase Boundary . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
12.3.5 Tip- and Filament-Assisted Deposition
at the Liquid–Liquid Interface . . . . . . . . . . . . . . . . . . . . . 449
12.4 Deposition with the Help of Tips . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
12.4.1 Deposition of Microcolumns by Using Microtips . . . . . 453