Title:
Bio-enabled syntheses of functional mineral oxide thin films

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Li, Yihong
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Sandhage, Kenneth H.
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Abstract
The bio-enabled syntheses of functional nano-structured metal oxide thin films is of importance for a range of applications, in photonics, electronics, sensing, cell engineering, and biochemical devices. This type of novel syntheses method can overcome problems common in conventional oxide processing. In general, conventional oxide processes often require thermal treatment, caustic chemicals, and mechanical processing when producing shape-controlled inorganic materials. In contrast, biological processes are usually carried out under mild conditions (low temperature, neutral pH, and atmospheric pressure) and are therefore promising for the development of benign processes. Functional materials synthesized at room temperature using biomolecules are promising due to their expediency. During recent years, significant discoveries and progress have been made in discovering, and finding new applications for such biomimetic oxide-based minerals. However, much of the research has focused on SiO- and TiO-bearing organic-inorganic hybrid materials, of which a significant limitation is that, there are relatively few water-soluble inorganic oxide precursors commercially available for such biological syntheses. Two common compounds that are used in the biomimetic syntheses of SiO₂ and TiO₂ are tetramethoxisilane (TMOS) and Ti(IV) -bis(ammonium lactato) dihydroxide ( TiBALDH ). As a result, approaches to synthesize new water-soluble transitional metal complexes for use as precursors in the biomineralization of the corresponding functional metal oxide thin films were explored in this work, in order to expand the range of functional oxide chemistries formed via bio-enabled methods. A Ti-containing compound was synthesized to compare the behavior of commercially-available and as-synthesized TiBALDH. Another titanium-containing complex with citrate ligands, instead of lactate, was also synthesized to investigate the influence of the ligand type on the deposition behavior of the precursors. Zirconium- and hafnium-containing complexes were also synthesized to demonstrate the feasibility and versatility of the idea of applying bio-enabled syntheses to the fabrication of functional mineral oxides other than the reported SiO₂ and TiO₂. The second part of this thesis focuses on developing a novel way to fabricate porous functional mineral oxide thin films with controlled pore size, which can be used in a variety of applications, such as dye loading for optical, photochemical, or electrochemical purposes. Commercially-available, carboxyl-group-terminated polystyrene spheres of different sizes were utilized as pore-size controllers in the bio-enabled syntheses of TiO₂ by protamine. This approach has been found to be an effective means of creating uniform pores in inorganic mineral oxide coatings. The accomplishments of this work have the potential to be integrated so as to expand the boundaries of biomineralization in materials science and engineering fields.
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2013-11-21
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