Advanced polymer thin films for functional materials via oxidative molecular layer deposition(oMLD)
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[EMBARGOED UNTIL 12/01/2026] The development of advanced functional thin films is essential for next-generation energy storage, water purification, and electronic devices. In this dissertation, oxidative molecular layer deposition (oMLD) is employed as a versatile, gas-phase technique for the conformal growth of semiconducting polymers with precise thickness control at the molecular scale. Building on the principles of self-limiting surface reactions, this work explores the synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (pPy), and related copolymers directly onto diverse substrates, including planar wafers, and porous scaffolds. Comprehensive in situ and ex situ characterization-- using quartz crystal microbalance (QCM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Raman spectroscopy--was conducted to elucidate the relationships between deposition parameters, reaction kinetics, and resulting film properties. The effects of precursor chemistry, substrate type, and process temperature on polymer growth rate, composition, morphology, and electrical conductivity are systematically examined. Thermal stability was assessed via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), revealing enhanced stability of oMLD-grown films compared to other common polymerization techniques. This research demonstrates that oMLD enables conformal polymer coatings with tunable composition and functionality, even within challenging 3D geometries, and highlights strategies to optimize electrical and structural performance. The findings advance the understanding of gas-phase polymer synthesis and open pathways for integrating conductive polymers into energy storage devices, desalination membranes, and thin-film electronic systems
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Ph. D.