No description available.

Recent advances in nanofabrication techniques have opened up new avenues and numerous possible applications in both nanoscale electrochemistry and analytical nanoscience by enabling the fabrication of reproducible nanoelectrodes with different new geometries. Nanoelectrodes exhibit advantages including enhanced mass transport, higher current densities, improved signal-to-noise ratios, and lower ohmic drop. In this dissertation, the use of nanoelectrodes in the electrochemical response properties investigations or in the spectroelectrochemical studies is the unifying factor among all the chapters. First (in Chapter 4), we presented a direct comparison between the electrochemical characteristics of two finite nanoelectrodes arrays with different geometries: 6 × 6 recessed nanodiscs and nanorings microarrays. Using computational methods, it was demonstrated that the electrode geometry’s parameters have a drastic influence on the mass transport properties of the nanoelectrodes. The results presented here are the first combination of experimental and numerical studies that elucidate the transport on nanoring electrode arrays. The comparison of the electrochemical behavior between nanostructures using full 3D simulations is also unique. Second, we have provided a comprehensive numerical study on the redox cycling performance properties of a 6 × 6 recessed nanorings-ring electrode array configuration. The simulation results were in good agreement with the experimental data. After validating the model against experiments, a comprehensive computational investigation revealed avenues to optimize the performance of the structure in terms of geometric parameters and scan rates. The second half of this dissertation is comprised of the spectroelectrochemical studies. The combination of surface plasmon resonance with electrochemistry presents new paths to investigateredox reaction events at the electrode surface since it brings an additional dimension to the classical electrochemical approaches. Third, we have reported a novel active plasmonic device based on a new switching mechanism for the nanohole electrodes array to bridge between photonics and electronics at nanoscales. The inner surfaces of the nanohole electrodes in the array were coated with an electroconductive polymer, polypyrrole, (PPy). Then, it was shown that light transmitted through the PPy- modified nanohole electrodes can be easily tuned and controled by applying an external potential. We were also able to switch on and off the transmitted light intensity through the modified nanohole arrays by potential steps, demonstrating the potential of this platform to be incorporated into optoelectronic devices. Finally, we have fabricated larger area plasmonic periodic nanopillar 3D electrodes using a rapid, high-throughput, and cost-effective approach: the laser interference lithography. Then, the electrochemical behavior of these electrodes was investigated both experimentally and computationally. The properties were ‘compared with a flat electrode with an equivalent geometric area. Afterward, we have successfully probed the changes in the concentration of a reversible redox pair near the electrode surface induced by various applied potentials, in an in-situ EC-SPR experiment. / Graduate

In this work, we study the use of a spatial light modulator (SLM) for local manipulation of phase in interfering laser beams to fabricate photonic crystal templates with embedded, engineered defects. A SLM displaying geometric phase patterns was used as a digitally programmable phase mask to fabricate 4-fold and 6-fold symmetric photonic crystal templates. Through pixel-by-pixel phase engineering, digital control of the phases of one or more of the interfering beams was demonstrated, thus allowing change in the interference pattern. The phases of the generated beams were programmed at specific locations, resulting in defect structures in the fabricated photonic lattices such as missing lattice line defects, and single-motif lattice defects in dual-motif lattice background. The diffraction efficiency from the phase pattern was used to locally modify the filling fraction in holographically fabricated structures, resulting in defects with a different fill fraction than the bulk lattice. Through two steps of phase engineering, a spatially variant lattice defect with a 90° bend in a periodic bulk lattice was fabricated. Finally, by reducing the relative phase shift of the defect line and utilizing the different diffraction efficiency between the defect line and the background phase pattern, desired and functional defect lattices can be registered into the background lattice through direct imaging of the designed phase patterns.

Abstract: When noble metals particles are synthesized with progressively smaller dimensions, strikingly novel optical properties arise. For nanoscale particles, collective disturbances of the electron density known as localized surface plasmons resonances can arise, and these resonances are utilized in a variety of applications ranging from surface-enhanced molecular spectroscopy and sensing to photothermal cancer therapy to plasmon-driven photochemistry. Central to all of these studies is the plasmon’s remarkable ability to process light, capturing and converting it into intense near fields, heat, and even energetic carriers at the nanoscale. In the past decade, we have witnessed major advances in plasmonics which is directly linked with the much broader field of (colloidal) nanotechnology. These breakthroughs span from plasmon lasing and waveguides, plasmonic photochemistry and solar cells to active plasmonics, plasmonics nanocomposites and semiconductor plasmons. All the above-mentioned phenomena rely on precise spatial placement and distinct control over the dimensions and orientation of the individual plasmonic building blocks within complex one-, two- or three-dimensional complex arrangements. For the nanofabrication of metal nanostructures at surfaces, most often lithographic approaches, e.g. e-beam lithography or ion-beam milling are generally applied, due to their versatility and precision. However, these techniques come along with several drawbacks such as limited scalability, limited resolution, limited compatibility with silicon manufacturing techniques, damping effects due to the polycrystalline nature of the metal nanostructures and low sample throughput. Thus, there is a great demand for alternative approaches for the fabrication of metal nanostructures to overcome the above-mentioned limitations. But why colloids? True three-dimensionality, lower damping, high quality modes due to mono-dispersity, and the absence of grain boundaries make the colloidal assembly an especially competitive method for high quality large-scale fabrication. On top of that, colloids provide a versatile platform in terms of size, shape, composition and surface modification and dispersion media. 540The combination of directed self-assembly and laser interference lithography is a versatile admixture of bottom-up and top-down approaches that represents a compelling alternative to commonly used nanofabrication methods. The objective of this thesis is to focus on large area fabrication of emergent spectroscopic properties with high structural and optical quality via colloidal self-assembly. We focus on synergy between optical and plasmonic effects such as: (i) coupling between localized surface plasmon resonance and Bragg diffraction leading to surface lattice resonance; (ii) strong light matter interaction between guided mode resonance and collective plasmonic chain modes leading to hybrid guided plasmon modes, which can further be used to boost the hot-electron efficiency in a semiconducting material; (iii) similarly, bilayer nanoparticle chains leading to chiro-optical effects. Following this scope, this thesis introduces a real-time tuning of such exclusive plasmonic-photonic (hybrid) modes via flexible template fabrication. Mechanical stimuli such as tensile strain facilitate the dynamic tuning of surface lattice resonance and chiro-optical effects respectively. This expands the scope to curb the rigidity in optical systems and ease the integration of such systems with flexible electronics or circuits.:Contents Abstract Kurzfassung Abbreviations 1. Introduction and scope of the thesis 1.1. Introduction 1.1.1. Classical optics concepts 1.1.2. Top down fabrication methods and their challenges 1.1.3. Template-assisted self-assembly 1.1.4. Functional colloidal surface assemblies 1.2. Scope of the thesis 2. Results and Discussion 2.1. Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly 2.1.1. Fabrication of flexible 2D plasmonic lattice 2.1.2. Investigation of the influence of particle size distribution on SLR quality 2.1.3. Band diagram analysis of 2D plasmonic lattice 2.1.4. Strain induced tuning of SLR 2.1.5. SEM and force transfer analysis in 2D plasmonic lattice under various strain 2.2. Hybridized Guided-Mode Resonances via Colloidal Plasmonic Self-Assembled Grating 2.2.1. Fabrication of hybrid opto-plasmonic structure via template assisted self-assembly 2.2.2. Comparison of optical band diagram of three (plasmonic, photonic and hybrid) different structures in TE and TM modes 2.2.3. Simulative comparison of optical properties of hybrid opto-plasmonic NP chains with a grating of metallic gold bars 2.2.4. Effect of cover index variation with water as a cover medium 2.3. Hot electron generation via guided hybrid modes 2.3.1. Fabrication of the hybrid GMR structure via LIL and lift-off process 2.3.2. Spectroscopic and simulative analysis of hybrid opto-plasmonic structures of different periodicities 2.3.3. Comparative study of photocurrent generation in different plasmonic structures 2.3.4. Polarization dependent response at higher wavelength 2.3.5. Directed self-assembly of gold nanoparticles within grating channels of a dielectric GMR structure supported by titanium dioxide film 2.4. Active Chiral Plasmonics Based on Geometrical Reconfiguration 2.4.1. Chiral 3D assemblies by macroscopic stacking of achiral chain substrates 3. Conclusion 4. Zusammenfassung 5. Bibliography 6. Appendix 6.1. laser interference lithography 6.2. Soft molding 6.3. Determine fill factor of plasmonic lattice 6.4. 2D plasmonic lattice of Au_BSA under strain 6.5. Characterizing order inside a 2D lattice 6.6. Template-assisted colloidal self-assembly 6.7. Out of plane lattice resonance in 1D and 2D lattices 6.8. E-Field distribution at out of plane SLR mode for 1D lattices of various periodicity with AOI 20° 6.9. Refractive index of PDMS and UV-PDMS 6.10. Refractive index measurement for sensing 6.11. Optical constants of TiO2, ma-N 405 photoresist and glass substrate measured from spectroscopic ellipsometry Acknowledgement/ Danksagung Erklärung & Versicherung List of Publications

A near-field technique known as evanescent interferometric lithography allows for high resolution imaging. However its primary limitation is that the image exponentially decays within the photoresist due to physical limits. This thesis aims to overcome this limitation and presents a method to considerably enhance the depth of focus of images created using evanescent interferometric lithography by using a material underlay beneath the photoresist. A key enabler of this is the understanding that evanescent fields couple to surface states and operating within proximity of a resonance, the strength of the coupling allows for considerable energy extraction from the incident beam and redistribution of this energy in a photoresist cavity. This led to the analysis of the Fresnel equations, which suggested that such coupling was in fact the result of an enhanced reflectance that takes place at boundaries of carefully chosen materials. While it is known that metals and lossy dielectrics result in surface plasmon polaritons (SPP) and surface exciton polaritons (SEP) as conventional solutions to the Fresnel reflection equations for the TM polarization of light, there is no such naturally occurring surface state that allows evanescent wave enhancement with the TE polarization of light. Further investigation of the Fresnel reflection equations revealed both for TM and TE that in fact another solution exists that is but unconventional to enhance the reflectivity. This solution requires that one of the media have a negative loss. This is a new type of surface resonance that requires that one of the media be a gain medium; not one in the optical pumped sense but one that would naturally supply energy to a wave to make it grow. This new surface resonance is also a key result of this thesis. Clearly, however this is only a hypothetical solution as a real gain medium would violate the conservation of energy. However, as it is only the reflectance of this gain medium that is useful for evanescent wave enhancement, in fact a multilayered stack consisting of naturally occurring materials is one way to achieve the desired reflectivity. This would of course be only an emulation of the reflectivity aspect of the gain medium. This multilayered stack is then an effective gain medium for the reflectivity purposes when imaging is carried out at a particular NA at a particular wavelength. This proposal is also a key idea of this thesis. At λ = 193 nm, this method was used to propose a feasible design to image high resolution structures, NA = 1.85 at an aspect ratio of ~3.2. To experimentally demonstrate the enhancements, a new type of solid immersion test bed, the solid immersion Lloyd's mirror interference lithography test-bed was constructed. High quality line and space patterns with a half-pitch of 55.5 nm were created using λ = 405 nm, corresponding to a NA of 1.824, that is well in the evanescent regime of light. Image depths of 33-40 nm were seen. Next, the evanescent image was coupled to an effective gain medium made up of a thin layer of hafnium oxide (HfO) upon silicon dioxide (SiO2). This resulted in a considerable depth enhancement, and 105 nm tall structures were imaged. The work in this thesis details the construction of the solid immersion lithography test-bed, describes the implementation of the modeling tools, details the theory and analysis required to achieve the relevant solutions and understanding of the physical mechanism and finally experimentally demonstrates an enhancement that allows evanescent interferometric lithography beyond conventional limits.