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Intro; Supervisor's Foreword; Thesis Declaration; Acknowledgements; Contents; Abbreviations; Symbols; List of Figures; List of Tables; Summary; 1 General Introduction; 1.1 Introduction; References; 2 Plasmonic Properties, Stability and Chemical Reactivity of Metal Nanoparticles-A Literature Review; 2.1 Introduction; 2.2 Engineering Sub-nm Gaps in Nanostructures for Applications in Plasmonics; 2.2.1 Top-Down Approach; 2.2.2 Bottom-Up Approach; 2.3 Characterization Techniques for the Charge Transfer Plasmon Mode; 2.3.1 Far-Field Optical Characterization
2.3.2 Near-Field Spectroscopy of Plasmons2.4 Stability of the Metal Nanoparticles Against Electron Beam Irradiation; 2.4.1 Electron Beam-Induced Damage; 2.4.2 Sintering Mechanisms for Dimers or Clusters of Nanoparticles; 2.4.3 Strategies to Control Damage Caused by Electron Beam; 2.5 Chemical Reactivity with Other Metal Ions in Solution; 2.5.1 Introduction to Liquid-Cell Electron Microscopy (LC-EM); 2.5.2 Engineering the Gold and Silver Nanostructures via Control of Elemental Composition; 2.5.2.1 Galvanic Replacement; 2.5.2.2 Core-Shell Nanostructures; 2.6 Conclusions and Outlook; References
3 Self-Assembly of Silver Nanoparticles with Sub-nanometer SeparationsAbstract; 3.1 Introduction; 3.2 Results and Discussion; 3.2.1 Synthesis and Functionalization of Silver Nanocubes; 3.2.2 Transmission Electron Microscope (TEM) Gap Size Characterization; 3.2.3 3D Scanning TEM Tomography; 3.2.4 UV-Visible (UV-Vis) Spectroscopy; 3.2.5 X-Ray and Ultraviolet Photoelectron Spectroscopy (XPS and UPS); 3.3 Conclusions; 3.4 Experimental Section; 3.4.1 General Procedures; 3.4.2 Synthesis of Silver Nanocubes; 3.4.3 Functionalization of Silver Nanocubes with Mixed SAMs; 3.4.4 Experimental Techniques
4.4.3 Functionalization of Silver Nanocubes with Mixed SAMs4.4.4 EELS Measurements; 4.4.5 Simulation Methods; References; 5 Stability of Silver and Gold Nanoparticles Under Electron Beam Irradiation; Abstract; 5.1 Introduction; 5.2 Results and Discussion; 5.2.1 Synthesis and Functionalization of Silver and Gold Nanocuboids; 5.2.2 Tunneling CTP Between Gold Nanocuboids; 5.2.3 Filament Formation Between Closely-Spaced Gold Nanocuboids; 5.2.4 The Role of Ligands; 5.3 Conclusions; 5.4 Experimental Section; 5.4.1 General Procedures; 5.4.2 Synthesis of Silver Nanocubes
2.3.2 Near-Field Spectroscopy of Plasmons2.4 Stability of the Metal Nanoparticles Against Electron Beam Irradiation; 2.4.1 Electron Beam-Induced Damage; 2.4.2 Sintering Mechanisms for Dimers or Clusters of Nanoparticles; 2.4.3 Strategies to Control Damage Caused by Electron Beam; 2.5 Chemical Reactivity with Other Metal Ions in Solution; 2.5.1 Introduction to Liquid-Cell Electron Microscopy (LC-EM); 2.5.2 Engineering the Gold and Silver Nanostructures via Control of Elemental Composition; 2.5.2.1 Galvanic Replacement; 2.5.2.2 Core-Shell Nanostructures; 2.6 Conclusions and Outlook; References
3 Self-Assembly of Silver Nanoparticles with Sub-nanometer SeparationsAbstract; 3.1 Introduction; 3.2 Results and Discussion; 3.2.1 Synthesis and Functionalization of Silver Nanocubes; 3.2.2 Transmission Electron Microscope (TEM) Gap Size Characterization; 3.2.3 3D Scanning TEM Tomography; 3.2.4 UV-Visible (UV-Vis) Spectroscopy; 3.2.5 X-Ray and Ultraviolet Photoelectron Spectroscopy (XPS and UPS); 3.3 Conclusions; 3.4 Experimental Section; 3.4.1 General Procedures; 3.4.2 Synthesis of Silver Nanocubes; 3.4.3 Functionalization of Silver Nanocubes with Mixed SAMs; 3.4.4 Experimental Techniques
4.4.3 Functionalization of Silver Nanocubes with Mixed SAMs4.4.4 EELS Measurements; 4.4.5 Simulation Methods; References; 5 Stability of Silver and Gold Nanoparticles Under Electron Beam Irradiation; Abstract; 5.1 Introduction; 5.2 Results and Discussion; 5.2.1 Synthesis and Functionalization of Silver and Gold Nanocuboids; 5.2.2 Tunneling CTP Between Gold Nanocuboids; 5.2.3 Filament Formation Between Closely-Spaced Gold Nanocuboids; 5.2.4 The Role of Ligands; 5.3 Conclusions; 5.4 Experimental Section; 5.4.1 General Procedures; 5.4.2 Synthesis of Silver Nanocubes