abstract: Electromigration (EM) has been a serious reliability concern in microelectronics packaging for close to half a century now. Whenever the challenges of EM are overcome newer complications arise such as the demand for better performance due to increased miniaturization of semiconductor devices or the problems faced due to undesirable properties of lead-free solders. The motivation for the work is that there exists no fully computational modeling study on EM damage in lead-free solders (and also in lead-based solders). Modeling techniques such as one developed here can give new insights on effects of different grain features and offer high flexibility in varying parameters and study the corresponding effects. In this work, a new computational approach has been developed to study void nucleation and initial void growth in solders due to metal atom diffusion. It involves the creation of a 3D stochastic mesoscale model of the microstructure of a polycrystalline Tin structure. The next step was to identify regions of current crowding or ‘hot-spots’. This was done through solving a finite difference scheme on top of the 3D structure. The nucleation of voids due to atomic diffusion from the regions of current crowding was modeled by diffusion from the identified hot-spot through a rejection free kinetic Monte-Carlo scheme. This resulted in the net movement of atoms from the cathode to the anode. The above steps of identifying the hotspot and diffusing the atoms at the hot-spot were repeated and this lead to the initial growth of the void. This procedure was studied varying different grain parameters. In the future, the goal is to explore the effect of more grain parameters and consider other mechanisms of failure such as the formation of intermetallic compounds due to interstitial diffusion and dissolution of underbump metallurgy. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

abstract: Nanocrystalline (NC) materials experience inherent microstructural instability when exposed to elevated temperature, deformation rates or loads over long periods of time which limits its applications as well as processing. The instability arises due to the predominance of grain boundary (GB) diffusional processes which hastens coarsening. This dissertation aims to provide a solution for the very first time, through the development and characterization of a bulk NC alloy system. The NC-Cu-Ta discussed here offers exceptional thermal stability in addition to superior strength and creep resistance. The systematic study of the behavior of this material will pave the way for future development of NC materials with a multitude of optimized properties for extreme applications. In-situ and ex-situ TEM characterization, multiple strain-rate compression testing and atomistic modeling were employed to investigate the behavior of NC-Cu-Ta under intense heating, stress/strain-rate and creep conditions. Results reveal, that temperature influences the misfit strain, leading to a significant change in flow stress, despite which (strength) remains greater than all known NC metals. Further, this alloy was found to achieve and retain strengths which were over two orders of magnitude higher than most NC metals under elevated temperature conditions. Dislocation-based slip was found to predominate at elevated temperatures for both high- and low-strain rate testing whereas twinning was favored during low temperature high-strain rate testing. The solute concentration was also found to play a role in dictating the deformation where heterogeneous twinnability was found to decrease with an increase in Ta concentration. A paradigm-shift in the creep response of NC-materials with unprecedented property combinations is also reported, i.e., high strength with extremely high temperature creep resistance (6-8 orders higher than other NC materials), in this NC-Cu-Ta-alloy. The unique combination of properties in these NC-alloys is achieved through a processing route that creates distinct GB-pinning nanoclusters of the solute that favor kinetic stability of grains. Overall, this dissertation provides an understanding of the mechanical response of a stable alloy system to extreme conditions, which was previously unattainable, and a perspective on the design of a new class of NC alloys exhibiting a multitude of optimized high temperature properties. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

abstract: Over the past several years, the density of integrated circuits has been increasing at a very fast rate, following Moore’s law. The advent of three dimensional (3D) packaging technologies enable the increase in density of integrated circuits without necessarily shrinking the dimensions of the device. Under such constraints, the solder volume necessary to join the various layers of the package is also extremely small. At smaller length scales, the local cooling rates are higher, so the microstructures are much finer than that obtained in larger joints (BGA, C4). The fraction of intermetallic compounds (IMCs) present in solder joints in these volumes will be larger. The Cu6Sn5 precipitate size and spacing, and Sn grain structure and crystallography will be different at very small volumes. These factors will most certainly affect the performance of the solder. Examining the mechanical behavior and reliability of Pb-free solders is difficult, primarily because a methodology to characterize the microstructure and the mechanics of deformation at these extremely small length scales has yet to be developed. In this study, Sn grain orientation and Cu6Sn5 IMC fraction, size, and morphology are characterized in 3D, in pure Sn based solder joints. The obtained results show differences in morphology of Sn grains and IMC precipitates as a function of location within the solder joint indicating influence of local cooling rate differences. Ex situ and in situ electromigration tests done on 250 um and 500 um pure Sn solder joints elucidate the evolution of microstructure, specifically Sn grain growth, IMC segregation and surface degradation. This research implements 3D quantification of microstructural features over micro and nano-scales, thereby enabling a multi-scale / multi-characterization approach. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

abstract: Dealloying, the selective electrochemical dissolution of an active component from an alloy, often results in nanoscale bi-continuous solid/void morphologies. These structures are attracting attention for a wide range of applications including catalysis, sensing and actuation. The evolution of these nanoporous structures has been widely studied for the case at low homologous temperature, TH, such as in Ag-Au, Cu-Au, Cu-Pt, etc. Since at low TH the solid-state mobility of the components is of order 10-30 cm2s-1 or less, percolation dissolution is the only mechanism available to support dealloying over technologically relevant time scales. Without the necessity of solid-state mass transport, percolation dissolution involves sharp transitions based on two key features, the parting limit and critical potential. Dealloying under conditions of high TH, (or high intrinsic diffusivity of the more electrochemically reactive component) is considerably more complicated than at low TH. Since solid-state mass transport is available to support this process, a rich set of morphologies, including negative or void dendrites, Kirkendall voids and bi-continuous porous structures, can evolve. In order to study dealloying at high TH we have examined the behavior of Li-Sn and Li-Pb alloys. The intrinsic diffusivities of Li were measured in these alloys using electrochemical titration and time of flight measurements. Morphology evolution was studied with varying alloy composition, host dimension and imposed electrochemical conditions. Owing to diffusive transport, there is no parting limit for dealloying, however, there is a compositional threshold (pPD) as well as a critical potential for the operation of percolation dissolution and the formation of bi-continuous structures. Negative or void dendrite morphologies evolve at compositions below pPD and at large values of the applied electrochemical potential when the rate of dealloying is limited by solid-state mass transport. This process is isomorphic to dendrite formation in electrodeposition. Kirkendall voiding morphologies evolve below the critical potential over the entire range of alloy compositions. We summarize our results by introducing dealloying morphology diagrams that we use to graphically illustrate the electrochemical conditions resulting in various morphologies that can form under conditions of low and high TH. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

abstract: Sn and Al alloys are widely used in various industries. Environmental-induced damage resulting in whiskering in Sn and corrosion in Al account for numerous failures globally every year. Therefore, for designing materials that can better withstand these failures, a comprehensive study on the characterization of the damage is necessary. This research implements advanced characterization techniques to study the above-mentioned environmental-induced damage in Sn and Al alloys. Tin based films are known to be susceptible to whisker growth resulting in numerous failures. While the mechanisms and factors affecting whisker growth have been studied extensively, not much has been reported on the mechanical properties of tin whiskers themselves. This study focuses on the tensile behavior of tin whiskers. Tensile tests of whiskers were conducted in situ a dual beam focused ion beam (FIB) with a scanning electron microscope (SEM) using a micro electro-mechanical system (MEMS) tensile testing stage. The deformation mechanisms of whiskers were analyzed using transmission electron microscopy (TEM). Due to the heterogenous nature of the microstructure of Al 7075, it is susceptible to corrosion forming corrosion products and pits. These can be sites for cracks nucleation and propagation resulting in stress corrosion cracking (SCC). Therefore, complete understanding of the corrosion damaged region and its effect on the strength of the alloy is necessary. Several studies have been performed to visualize pits and understand their effect on the mechanical performance of Al alloys using two-dimensional (2D) approaches which are often inadequate. To get a thorough understanding of the pits, it is necessary for three-dimensional (3D) studies. In this study, Al 7075 alloys were corroded in 3.5 wt.% NaCl solution and X-ray tomography was used to obtain the 3D microstructure of pits enabling the quantification of their dimensions accurately. Furthermore, microstructure and mechanical property correlations helped in a better understanding of the effect of corrosion. Apart from the pits, a surface corrosion layer also forms on Al. A subsurface damage layer has also been identified that forms due to the aggressive nature of NaCl. Energy dispersive X-ray spectroscopy (EDX) and nanoindentation helped in identifying this region and understanding the variation in properties. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

abstract: Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i.e. Pd3O3, enables the fabrication of stable devices achieving nearly 1000h. at 1000cd/m2 without any outcoupling enhancement while simultaneously achieving peak external quantum efficiencies of 19.9%. Chapter 4 discusses tetradentate platinum and palladium complexes as deep blue emissive materials for display and lighting applications. The platinum complex PtNON, achieved a peak external quantum efficiency of 24.4 % and CIE coordinates of (0.18, 0.31) in a device structure designed for charge confinement and the palladium complexes Pd2O2 exhibited peak external quantum efficiency of up to 19.2%. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

abstract: My research has been focusing on the innovations of material and structure designs, and the development of fabrication processes of novel nanoelectronics devices. My first project addresses the long-existing challenge of implantable neural probes, where high rigidity and high flexibility for the probe need to be satisfied at the same time. Two types of probes that can be used out of the box have been demonstrated, including (1) a compact probe that spontaneously forms three-dimensional bend-up devices only after implantation, and (2) an ultra-flexible probe as thin as 2 µm attached to a small silicon shaft that can be accurately delivered into the tissue and then get fully released in situ without altering its shape and position as the support is fully retracted. This work provides a general strategy to prepare ultra-small and flexible implantable probes that allow high insertion accuracy and minimal surgical damages with best biocompatibility. My second project focuses on the injection and characterization of carrier spins in single crystal diamond based nanoscale devices. The conventional diamond-based quantum information process that exploits nitrogen vacancy centers faces a major barrier of large scale communication. Electron/hole spin in diamond devices, on the other hand, could also be a good candidate for quantum computing due to the very small spin-orbit coupling and great coherent transport length of spin. To date, there has been no demonstration of carrier spin transport in diamond. In this work, I try to answer this fundamental question of how to inject and characterize electron spins in Boron doped diamond. Nanoscale diamond devices have been fabricated to investigate this question, including Hall bar device for material characterization, and lateral spin valve for injecting spin-polarized current into a mesoscopic diamond bar and detecting induced pure spin current. The preliminary results show signatures of spin transport in heavily doped diamond films. Looking into the future, the knowledge we obtained in these two projects, including the strategy to integrate thin-film nanoelectronics devices on a flexible bio-probe configuration, and how to build spintronic devices with diamond structures, could be unified in the exploration of spin-based sensors in biological systems. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

abstract: A major obstacle to sustainable solar technologies is end-of-life solar modules. In this thesis, a recycling process is proposed for crystalline-Si solar modules. It is a three-step process to break down Si modules and recover various materials. Over 95% of a module by weight can be recovered with this process. Two new technologies are demonstrated to enable the proposed recycling process. One is sequential electrowinning which allows multiple metals to be recovered one by one from Si modules, Ag, Pb, Sn and Cu. The other is sheet resistance monitoring by the 4-point probe which maximizes the amount of solar-grade Si recovered from Si modules with high throughput. The purity of the recovered metals is above 99% and the recovery rate can achieve between 70~80%. The recovered Si meets the specifications for solar-grade Si and at least 91% of Si from c-Si solar cells can be recovered. The recovered Si and metals are new feedstocks to the solar industry and generate over $12/module in revenue. This revenue enables a profitable recycling business for Si modules without any government support. The chemicals for recycling are carefully selected to minimize their environmental impact and also the cost. A network for collecting end-of-life solar modules is proposed based on the current distribution network for solar modules to contain the collection cost. As a result, the proposed recycling process for c-Si modules is technically, environmentally and financially sustainable. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

abstract: Doping and alloying agents are commonly used to engineer the properties of magnetic materials. This study investigates the effects of doping manganese in thin films of Ni80Fe20 (permalloy) and Ni65Fe15Co20 magnetic systems for low power memory technologies, including those that operate at low temperature. Elemental manganese is anti-ferromagnetic with a Neel temperature of 100 K. When used as a dopant in a magnetic material, it is found to often align its moment in an antiferromagnetic direction. Thus, the addition of manganese might be expected to reduce the overall saturation magnetization (MS) of the magnetic system. In this study, we show that the use of manganese dopants in Ni80Fe20 (permalloy) and Ni65Fe15Co20 thin films can reduce their saturation magnetization and still retain excellent switching properties. Magnetic properties and transport properties were determined using Vibrating Sample Magnetometer. A 19% decrease in the MS of (Ni80Fe20)1-xMnx thin films and a 36% decrease for (Ni65Fe15Co20)1-xMnx thin films for dopant levels of x = 30%. The impact of depositing a ruthenium (Ru) under-layer for (Ni65Fe15Co20)1-xMnx system was also studied. The structural (lattice parameters and phases), surface (roughness and topography) and electrical properties (resistivity and mean free path) of the Mn-doped Ni65Fe15Co20 films were determined with X-Ray Diffraction, Atomic Force Microscopy and Four-Point probe technique respectively. The properties were analyzed and Ni65Fe15Co20 system with Ru- under-layer with 20 at. % Mn content was found to exhibit the following low-field switching properties at 10 K; MS~700 emu.cm-3, easy axis coercivity ~10 Oe and hard axis coercivity ~5 Oe, easy axis squareness ~0.9 and anisotropy field ~12 Oe, that are deemed useful for low-power memory applications that could be used at cryogenic temperatures. To determine the transport properties thought these magnetic layers for use in superconductor/ferromagnetic memory structures, a study of the oxidation conditions of Al films was performed in order to produce a reliable aluminum oxide tunnel barrier on top of these films. The production of N-I-F-S (Normal metal-Insulator-Ferromagnet-Superconductor) tunnel junctions will allow for the investigation of the tunneling density of states as a function of ferromagnetic layer thickness, allowing for the determination of important transport parameters relevant to magnetic barrier Josephson junction devices. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2018

abstract: Diamond and cubic boron nitride (c-BN) are ultra wide band gap semiconductors (Eg>3.4 eV) and share similar properties in various aspects, including being isoelectronic, a 1% lattice mismatch, large band gap, high thermal conductivity. Particularly, the negative electron affinity (NEA) of diamond and c-BN is an unusual property that has led to effects such as p-type surface conductivity, low temperature thermionic emission, and photon enhanced thermionic emission. In this dissertation, the interface chemistry and electronic structure of dielectrics on diamond and c-BN are investigated with X-ray and ultraviolet photoemission spectroscopy (XPS and UPS). The first study established that the surface conductive states could be established for thin Al2O3 on diamond using a post deposition H-plasma process. At each step of the atomic layer deposition (ALD) and plasma processing, the band alignment was characterized by in situ photoemission and related to interface charges. An interface layer between the diamond and dielectric layer was proposed to explain the surface conductivity. The second study further investigated the improvement of the hole mobility of surface conductive diamond. A thin layer of Al2O3 was employed as an interfacial layer between surface conductive hydrogen-terminated (H-terminated) diamond and MoO3 to increase the distance between the hole accumulation layer in diamond and negatively charged states in acceptor layer. With an interfacial layer, the ionic scattering, which was considered to limit the hole mobility, was reduced. By combining two oxides (Al2O3 and MoO3), the hole mobility and concentration were modulated by altering the thickness of the Al2O3 interfacial layer. The third study focused on the electronic structure of vanadium-oxide-terminated c-BN surfaces. The vanadium-oxide-termination was formed on c-BN by combining vanadium deposition using molecular beam deposition (MBD) and oxygen plasma treatment. After thermal annealing, a thermally stable NEA was achieved on c-BN. A model was proposed based on the deduced interface charge distribution to explain the establishment of an NEA. / Dissertation/Thesis / Doctoral Dissertation Physics 2018