Atomic layer deposition (ALD) is a thin film growth technique that relies on self-limiting reactions between vapor precursors and a surface.... Show moreAtomic layer deposition (ALD) is a thin film growth technique that relies on self-limiting reactions between vapor precursors and a surface. Significant progress has been made in the scope of materials grown by ALD, enabled by precursor development and investigation of surface reaction mechanisms; progress is still necessary. This dissertation has two portions. The first is the development of organometallic compounds to engender new material growth by ALD. Second is the development of X-ray absorption spectroscopy (XAS) tools and techniques for observations of the metal coordination environment during ALD. One material that can be difficult to make is doped materials. Composition of a doped material determines the film properties. One example is vanadium doped indium sulfide. This material was purposed as an intermediate bandgap solar absorbing material which can absorb multiple ranges of light. Two new precursors were developed for the growth of indium sulfide and vanadium sulfide. The indium sulfide material grown has shown superior film photocurrent qualities and doping of vanadium into indium sulfide with fine control over atomic placement was achieved. Films were grown that showed secondary absorptions which aligned with theoretical calculations. The flexibility of the V(III) precursor is shown by a short study on the control of the difficult vanadium-oxygen system in the deposition of stoichiometric oxides. To illustrate how XAS can be used in conjunction with other techniques tin dioxide growth from a stannylene precursor and hydrogen peroxide was studied. From ex situ XAS measurements nucleation, growth and termination reaction mechanism were discovered. Next, a mobile ALD reactor allowed for in situ XAS measurements to be performed on “flat” substrates for the first time. Specifically, the local coordination environment and surface reactions were followed while erbium was doped into alumina and coordination environment of manganese was investigated in the growth of manganese-doped zinc oxide, with the ability to probe in-plane versus out-of-plane bonds. These unique in situ XAS experiments allow for greater understand of metal and non-metal precursors as they interact with surfaces. This enhanced understanding enables new precursor development which leads to better control over surface chemistry and new materials. Ph.D. in Chemistry, July 2016 Show less
