The columnar microstructure of most thermally evaporated thin films detrimentally affects many of their properties through a reduction in packing density. In this work, we have investigated ion-assisted deposition as a means of disrupting this columnar growth for a number of coating materials. A Kaufman hot-cathode ion source bombarded thermally evaporated films with low-energy (< 1000 eV) positive ions during deposition in a cryopumped box coater. We have investigated MgF₂, Na₃AIF₆, AIF₃, LaF₃, CeF₃, NdF₃, Al₂O₃, and AIN. Argon ion bombardment of the fluoride coatings increased their packing densities dramatically. We achieved packing densities near unity without significant absorption for MgF₂, LaF₃, and NdF₃, while Na₃AIF₆, AIF₃, and CeF₃ began to absorb before unity packing density could be achieved. Fluorine was preferentially sputtered by the ion bombardment, creating anion vacancies. The films adsorbed water vapor and hydroxyl radicals from the residual chamber atmosphere. These filled the vacancy sites, eliminating absorption in the visible, but the oxygen complexes caused increased absorption in the ultraviolet. For LaF₃ and NdF₃, a sufficient amount of oxygen caused a phase transformation from the fluoride phase to an oxyfluoride phase. The refractive indices of Al₂O₃ films increased with ion bombardment. Values as high as 1.70 at 350 nm were achieved with bombardment by 500 eV oxygen ions. Since all of the Al₂O₃ films had packing densities near unity and were amorphous, we postulate that the increase in refractive index was due to a change in amorphous networking. Aluminum nitride was deposited by bombarding thermally evaporated aluminum with nitrogen ions. Films with N:Al ratios of 0.5-1.5 could be deposited by varying the deposition conditions. Films with low absorption for wavelengths longer than 1 μm could be deposited. Annealing the films at 500°C eliminated absorption at wavelengths longer than 500 nm.

The development of materials for optical thin film application is essential to progress in fields such as optical data storage and signal processing. Samarium sulfide (SmS) thin films were prepared by reactive evaporation of samarium in hydrogen sulfide (H₂S). These displayed optical switching properties despite the presence of large amounts of carbon and oxygen. They are therefore potentially useful for data storage. The semiconductor to metal phase transition was characterized by x-ray diffraction and spectrophotometry. The observed optical response was modelled by a Bruggeman effective medium calculation. Success with this analysis suggests it as a means for predicting performance in subsequent applications. Zinc sulfide (ZnS) thin films were prepared by molecular beam epitaxy (MBE). Implimentation of an H₂S treated silicon surface provided good chemical bond match in addition to a good lattice match. Atomic layer epitaxy was unsuccessfully explored as a means to grow ZnS from zinc and H₂S reactants, therefore other reactants are proposed. Both the MBE and ALE work is directed at the long term goals of producing p-type ZnS, which is suitable for semiconductor lasing at short wavelengths, and high quality SmS thin films.

The semiconducting sulphosalt Wittichenite has been identified as a possible absorber material for thin film photovoltaic devices. It has the chemical formula Cu3BiS3 and its component elements are those of low toxicity and high abundance making it a very attractive prospect for photovoltaic devices. The copper bismuth sulphur material system is not very well understood and information on it limited to a few small regions. To aid understanding of this system a pseudo-binary phase diagram along the CuS-Bi join of the Cu-Bi-S ternary phase diagram was constructed by making bulk samples of various compositions along the join and analysing them using X-ray diffraction and differential scanning calorimetry. This join was chosen because is crosses the point at which Cu3BiS3 would be expected to occur due to its stoichiometry. The CuS-Bi phase diagram shows Cu3BiS3 forms across a wide compositional range but is mixed with either bismuth metal or copper sulphides depending on composition. Films of Cu3BiS3 were made using sputtered copper and bismuth films annealed in a sulphur atmosphere and thermal co- evaporation of copper sulphide and bismuth.

published_or_final_version / Physics / Doctoral / Doctor of Philosophy

published_or_final_version / Mechanical Engineering / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Physics / Doctoral / Doctor of Philosophy

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