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Scanning Laser Epitaxy (SLE) is a new layer-by-layer additive manufacturing process being developed in the Direct Digital Manufacturing Laboratory at Georgia Tech. SLE allows for the fabrication of three-dimensional objects with specified microstructure through the controlled melting and re-solidification of a metal powder placed atop a base substrate. This dissertation discusses the work done to date on assessing the feasibility of using SLE to both repair single crystal (SX) turbine airfoils and manufacture functionally graded turbine components. Current processes such as selective laser melting (SLM) are not able to create structures with defined microstructure and often have issues with warping of underlying layers due to the high temperature gradients present when scanning a high power laser beam. Additionally, other methods of repair and buildup have typically been plagued by crack formation, equiaxed grains, stray grains, and grain multiplication that can occur when dendrite arms are separated from their main dendrites due to remelting. In this work, it is shown that the SLE process is capable of creating fully dense, crack-free equiaxed, directionally-solidified, and SX structures. The SLE process, though, is found to be currently constrained by the cumbersome method of choosing proper parameters and a relative lack of repeatability. Therefore, it is hypothesized that a real-time feedback control scheme based upon a robust offline model will be necessary both to create specified defect-free microstructures and to improve the repeatability of the process enough to allow for multi-layer growth. The proposed control schemes are based upon temperature data feedback provided at high frame rate by a thermal imaging camera. This data is used in both PID and model reference adaptive control (MRAC) schemes and drives the melt pool temperature during processing towards a reference melt pool temperature that has been found to give a desired microstructure in the robust offline model of the process. The real-time control schemes will enable the ground breaking capabilities of the SLE process to create engine-ready net shape turbine components from raw powder material.

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Defects in the functional oxides play an important role in electronic devices like metal oxide semiconductor field effect transistors (MOSFETs) and resistive random-access memories (ReRAMs). The continuous scaling of CMOS has brought the Si MOSFET to its physical technology limit and the replacement of Si channel with Ge channel is required. However, the performance of Ge MOSFETs suffers from Ge/oxide interface quality and reliability problems, which originates from the charge traps and defect states in the oxide or at the Ge/oxide interface. The sub-oxide layers composed of GeII states at the Ge/GeO2 interface seems unavoidable with normal passivation methods like hydrogen treatment, which has poor electrical properties and is related to the reliability problem. On the other hand, ReRAM works by formation and rupture of O vacancy conducting filaments, while how this process happens in atomic scale remains unclear. In this thesis, density functional theory is applied to investigate the defect behaviours in oxides to address existing issues in these electronic devices. In chapter 3, the amorphous atomic structure of doped GeO2 and Ge/GeO2 interface networks are investigated to explain the improved MOSFET reliability observed in experiments. The reliability improvement has been attributed to the passivation of valence alternation pair (VAP) type O deficiency defects by doped rare earth metals. In chapter 4, the oxidation mechanism of GeO2 is investigated by transition state simulation of the intrinsic defect diffusion in the network. It is proposed that GeO2 is oxidized from the Ge substrate through lattice O interstitial diffusion, which is different from SiO2 which is oxidized by O2 molecule diffusion. This new mechanism fully explains the strange isotope tracer experimental results in the literature. In chapter 5, the Fermi level pinning effect is explored for metal semiconductor electrical contacts in Ge MOSFETs. It is found that germanides show much weaker Fermi level pinning than normal metal on top of Ge, which is well explained by the interfacial dangling bond states. These results are important to tune Schottky barrier heights (SBHs) for n-type contacts on Ge for use on Ge high mobility substrates in future CMOS devices. In chapter 6, we investigate the surface and subsurface O vacancy defects in three kinds of stable TiO2 surfaces. The low formation energy under O poor conditions and the +2 charge state being the most stable O vacancy are beneficial to the formation and rupture of conducting filament in ReRAM, which makes TiO2 a good candidate for ReRAM materials. In chapter 7, we investigate hydrogen behaviour in amorphous ZnO. It is found that hydrogen exists as hydrogen pairs trapped at oxygen vacancies and forms Zn-H bonds. This is different from that in c-ZnO, where H acts as shallow donors. The O vacancy/2H complex defect has got defect states in the lower gap region, which is proposed to be the origin of the negative bias light induced stress instability.

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