Conformal sol-gel coatings on three-dimensional nanostructured templates.

摘要

Sol-gel processing techniques, such as spin coating and dip coating, have successfully been utilized over the past several decades to apply conformal coatings on planar substrates; however, controlled film growth on three-dimensional (3-D) nanostructured templates using the sol-gel process remains a significant challenge. Obstacles such as, uncontrolled hydrolyzation and condensation of metal alkoxide precursors on nanostructured surfaces are a few of the obstacles which lead to coatings with undesirable thicknesses and excess inorganic particles. A little over a decade ago, a surface sol-gel process was developed which utilizes stepwise film growth of anhydrous metal alkoxide precursors with hydroxylated surfaces. The surface sol-gel process provides control over the applied coating thickness and is viewed as a wet chemical analog to atomic layer deposition (ALD).;The work presented in this dissertation has focused on applying conformal sol-gel derived coatings with controlled thicknesses on 3-D nanostructured templates. The templates utilized in this work were derived from biological species, such as diatoms and butterflies, as well as a synthetic photoresist polymer (SU-8). Coatings were applied on the templates using a conventional reflux/evaporation deposition process and a custom-built computer controlled surface sol-gel pumping system. The coatings applied using the reflux/evaporation process yielded conformal coatings with uncontrolled film thicknesses whereas the coatings applied using the surface sol-gel process yielded conformal coatings with controlled thicknesses.;Barium titanate and europium-doped barium titanate coatings were applied on diatom frustules using the reflux/evaporation deposition process. The silica-based diatom frustules had to first be converted into magnesia/silicon composite replicas using a gas/solid displacement reaction to render the template chemically compatible with the barium titanate-based coating. Conformal titanate-based coatings were obtained on the magnesia frustule replicas possessing uncontrolled thicknesses and excess inorganic particles using the reflux/evaporation deposition process. The europium-doped barium titanate coated frustules exhibited bright red photoluminescent properties upon stimulation with an ultraviolet light source.;Silica-based diatom frustules were also utilized as 3-D nanostructured templates for fabrication of a micro-scale nitric oxide gas sensor. Tin oxide coatings were applied on the silica frustules using the automated surface sol-gel pumping system. An organic dendrimer method was developed for amplifying hydroxyl groups on the silica frustule surfaces to enhance the surface sol-gel deposition process. Conformal coatings with controlled thicknesses were obtained on the hydroxyl amplified frustule surfaces; however, little if any deposition was observed on the frustules that were not subjected to the hydroxyl amplification process. A single tin oxide coated diatom frustule served as a gas sensor component which was sensitive to very low concentrations of nitric oxide gas.;The automated surface sol-gel system was also used to apply multicomponent tin oxide-doped titania alkoxide chemistries on the wing scales of a blue Morpho butterfly. The alkoxide solutions reacted directly with the OH functionalities provided by the native chitin chemistry of the scales. The tin oxide served as a rutile nucleating agent which allowed the titania to completely crystallize in the high refractive index rutile titania phase with doping concentrations of tin oxide as low as 7 mol% after annealing at 450°C. The tin oxide-doped titania coatings were both nanocrystalline and nanothick and replicated the nanostructured scales with a high degree of accuracy. Undoped titania coatings applied on the scales required a heat treatment of 900°C to crystallize the coating in the rutile titania phase which led to adverse coarsening effects which destroyed the nanostructed features of the scales.;Tin oxide-doped titania coatings were also deposited on synthetic polymer (SU-8) photonic crystal structures using the automated surface sol-gel process. The hydroxyl concentration on the SU-8 surface was amplified using tris(hydroxymethyl)amino-methane which decreased the hydrophobicity of the SU-8 template and provided reactive OH functionalities for surface sol-gel deposition of the tin oxide-doped titania alkoxide precursor. The coating was crystallized in an acidic solution at 80°C which led to the formation of rutile titania inverse opal photonic crystal structures which maintained the overall structure and ordering of the template. The underlying SU-8 template was successfully removed using an oxygen plasma etch.