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Chemically Modified Metal Oxide Nanostructures Electrodes for Sensing and Energy ConversionElhag, Sami January 2017 (has links)
The goal of this thesis is the development of scalable, low cost synthesis of metal oxide nanostructures based electrodes and to correlate the chemical modifications with their energy conversion performance. Methods in energy conversion in this thesis have focused on two aspects; a potentiometric chemical sensor was used to determine the analytical concentration of some components of the analyte solution such as dopamine, glucose and glutamate molecules. The second aspect is to fabricate a photo-electrochemical (PEC) cell. The biocompatibility, excellent electro-catalytic activities and fast electron transfer kinetics accompanied with a high surface area to volume ratio; are properties of some metal oxide nanostructures that of a potential for their use in energy conversion. Furthermore, metal oxide nanostructures based electrode can effectively be improved by the physical or a chemical modification of electrode surface. Among these metal oxide nanostructures are cobalt oxide (Co3O4), zinc oxide (ZnO), and bismuth-zincvanadate (BiZn2VO6) have all been studied in this thesis. Metal oxide nanostructures based electrodes are fabricated on gold-coated glass substrate by low temperature (< 100 0C) wet chemicalapproach. X-ray diffraction, x-ray photoelectron spectroscopy and scanning electron microscopy were used to characterize the electrodes while ultraviolet-visible absorption and photoluminescence were used to investigate the optical properties of the nanostructures. The resultant modified electrodes were tested for their performance as chemical sensors and for their efficiency in PEC activities. Efficient chemically modified electrodes were demonstrated through doping with organic additives like anionic, nonionic or cationic surfactants. The organic additives are showing a crucial role in the growth process of metal oxide nanocrystals and hence can beused to control the morphology. These organic additives act also as impurities that would significantly change the conductivity of the electrodes. However, no organic compounds dependence was observed to modify the crystallographic structure. The findings in this thesis indicate the importance of the use of controlled nanostructures morphology for developing efficient functional materials.
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MORPHOLOGY TUNING OF OXIDE-METAL VERTICALLY ALIGNED NANOCOMPOSITES FOR HYBRID METAMATERIALSJuanjuan Lu (17658789) 19 December 2023 (has links)
<p dir="ltr">Metamaterials are artificially engineered nanoscale systems with a three-dimensional repetitive arrangement of certain components, and present exceptional optical properties for applications in nanophotonics, solar cells, plasmonic devices, and more. Self-assembled oxide-metal vertically aligned nanocomposites (VANs), with metallic phase as nanopillars embedded in the matrix oxide, have been recently proposed as a promising candidate for metamaterial applications. However, precise microstructural control and the structure-property relationships in VANs are still in high demand. Thus, by employing multiple approaches for structural design, this dissertation attempts to investigate the mechanisms of nanostructure evolutions and the corresponding optical responses.</p><p dir="ltr">In this dissertation, the precise control over the nanostructures has been demonstrated through morphology tuning, nanopillar orderings, and strain engineering. Firstly, Au, a well-known plasmonic mediator, has been selected as the metallic phase that forms nanopillars. Based on the previously proposed strain compensation model which describes the basic formation mechanism of VAN morphology, two oxides were then considered: La<sub>0.7</sub>Sr<sub>0.3</sub>MnO<sub>3 </sub>(LSMO) and CeO<sub>2</sub>. In the first two chapters of this dissertation, LSMO was considered due to its similar lattice (a<sub>LSMO </sub>= 3.87 Å, a<sub>Au </sub>= 4.08 Å) and its enormous potential in nanoelectronics and spintronics. Deposited on SrTiO<sub>3</sub> (001) substrate through pulsed laser deposition (PLD), LSMO-Au nanocomposites exhibit ideal VAN morphology as well as promising hyperbolic dispersions in response to the incident illuminations. By substrate surface treatment of annealing at 1000°C, and variation of STO substate orientations from (001), to (111) and (110), the improved and tunable in-plan orderings of Au nanopillars have been successfully achieved. In the third chapter, a new oxide-metal VAN system of <a href="" target="_blank">CeO<sub>2</sub></a>-Au (a<sub>CeO2 </sub>= 5.411 Å, and a<sub> CeO2</sub>/= 3.83 Å) has been deposited. The intriguing 45° rotated in-plan epitaxy presents an unexpected update to the strain compensation model, and tuning of Au morphology from nanopillars, nanoantennas, to nanoparticles also shows an effective modulation of the LSPR responses. COMSOL simulations have been exploited to reveal the relationships between Au morphologies and optical responses. In the last chapter, the two VAN systems of LSMO-Au and CeO<sub>2</sub>-Au have been combined to form a complex layered VAN thin film. Investigations into the strain states, the nature of complex interfaces, and the according hybrid properties, show dramatic possibilities for further strain engineering. In summary, this dissertation has provided multiple routes for highly tailorable oxide-metal nanocomposite designs. And the two proposed material systems present great potential in optical metamaterial applications including biosensors, photovoltaics, super lenses, and more.</p>
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