Matching Items (85)
Description
This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice matching with ZnSnP2, the other component in this tandem device. This work is divided into two main chapters, which will cover: calculations and method to determine the formation energy and abundance of native point defects, and a model to calculate the vapor pressure over a ternary material from first-principles. The purpose of this work is to guide experimental work being done in tandem to synthesize ZnGeAs2 in thin-film form with high enough quality such that it can be used as a photovoltaic. Since properties of photovoltaic depend greatly on defect concentrations and film quality, a theoretical understanding of how laboratory conditions affect these properties is very valuable. The work done here is from first-principles and utilizes density functional theory using the local density approximation. Results from the native point defect study show that the zinc vacancy (VZn) and the germanium antisite (GeZn) are the more prominent defects; which most likely produce non-stoichiometric films. The vapor pressure model for a ternary system is validated using known vapor pressure for monatomic and binary test systems. With a valid ternary system vapor pressure model, results show there is a kinetic barrier to decomposition for ZnGeAs2.
ContributorsTucker, Jon R (Author) / Van Schilfgaarde, Mark (Thesis advisor) / Newman, Nathan (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2011
Description
In an effort to begin validating the large number of discovered candidate biomarkers, proteomics is beginning to shift from shotgun proteomic experiments towards targeted proteomic approaches that provide solutions to automation and economic concerns. Such approaches to validate biomarkers necessitate the mass spectrometric analysis of hundreds to thousands of human samples. As this takes place, a serendipitous opportunity has become evident. By the virtue that as one narrows the focus towards "single" protein targets (instead of entire proteomes) using pan-antibody-based enrichment techniques, a discovery science has emerged, so to speak. This is due to the largely unknown context in which "single" proteins exist in blood (i.e. polymorphisms, transcript variants, and posttranslational modifications) and hence, targeted proteomics has applications for established biomarkers. Furthermore, besides protein heterogeneity accounting for interferences with conventional immunometric platforms, it is becoming evident that this formerly hidden dimension of structural information also contains rich-pathobiological information. Consequently, targeted proteomics studies that aim to ascertain a protein's genuine presentation within disease- stratified populations and serve as a stepping-stone within a biomarker translational pipeline are of clinical interest. Roughly 128 million Americans are pre-diabetic, diabetic, and/or have kidney disease and public and private spending for treating these diseases is in the hundreds of billions of dollars. In an effort to create new solutions for the early detection and management of these conditions, described herein is the design, development, and translation of mass spectrometric immunoassays targeted towards diabetes and kidney disease. Population proteomics experiments were performed for the following clinically relevant proteins: insulin, C-peptide, RANTES, and parathyroid hormone. At least thirty-eight protein isoforms were detected. Besides the numerous disease correlations confronted within the disease-stratified cohorts, certain isoforms also appeared to be causally related to the underlying pathophysiology and/or have therapeutic implications. Technical advancements include multiplexed isoform quantification as well a "dual- extraction" methodology for eliminating non-specific proteins while simultaneously validating isoforms. Industrial efforts towards widespread clinical adoption are also described. Consequently, this work lays a foundation for the translation of mass spectrometric immunoassays into the clinical arena and simultaneously presents the most recent advancements concerning the mass spectrometric immunoassay approach.
ContributorsOran, Paul (Author) / Nelson, Randall (Thesis advisor) / Hayes, Mark (Thesis advisor) / Ros, Alexandra (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013
Description
Signal processing techniques have been used extensively in many engineering problems and in recent years its application has extended to non-traditional research fields such as biological systems. Many of these applications require extraction of a signal or parameter of interest from degraded measurements. One such application is mass spectrometry immunoassay (MSIA) which has been one of the primary methods of biomarker discovery techniques. MSIA analyzes protein molecules as potential biomarkers using time of flight mass spectrometry (TOF-MS). Peak detection in TOF-MS is important for biomarker analysis and many other MS related application. Though many peak detection algorithms exist, most of them are based on heuristics models. One of the ways of detecting signal peaks is by deploying stochastic models of the signal and noise observations. Likelihood ratio test (LRT) detector, based on the Neyman-Pearson (NP) lemma, is an uniformly most powerful test to decision making in the form of a hypothesis test. The primary goal of this dissertation is to develop signal and noise models for the electrospray ionization (ESI) TOF-MS data. A new method is proposed for developing the signal model by employing first principles calculations based on device physics and molecular properties. The noise model is developed by analyzing MS data from careful experiments in the ESI mass spectrometer. A non-flat baseline in MS data is common. The reasons behind the formation of this baseline has not been fully comprehended. A new signal model explaining the presence of baseline is proposed, though detailed experiments are needed to further substantiate the model assumptions. Signal detection schemes based on these signal and noise models are proposed. A maximum likelihood (ML) method is introduced for estimating the signal peak amplitudes. The performance of the detection methods and ML estimation are evaluated with Monte Carlo simulation which shows promising results. An application of these methods is proposed for fractional abundance calculation for biomarker analysis, which is mathematically robust and fundamentally different than the current algorithms. Biomarker panels for type 2 diabetes and cardiovascular disease are analyzed using existing MS analysis algorithms. Finally, a support vector machine based multi-classification algorithm is developed for evaluating the biomarkers' effectiveness in discriminating type 2 diabetes and cardiovascular diseases and is shown to perform better than a linear discriminant analysis based classifier.
ContributorsBuddi, Sai (Author) / Taylor, Thomas (Thesis advisor) / Cochran, Douglas (Thesis advisor) / Nelson, Randall (Committee member) / Duman, Tolga (Committee member) / Arizona State University (Publisher)
Created2012
Description
This thesis is a qualitative research study that focuses on siblings of children with Autistic Spectrum Disorder (ASD). Even though it is expected that having a child with ASD in the family will influence the whole family including siblings of the child with ASD, the sibling population is rarely included in research related to children with ASD, and there is only limited services available for them. This exploratory study (n=6) is aimed at better understanding the siblings' lives in their family settings in order to identify the siblings' unmet needs and determine how they have been influenced by the child with ASD. This study is also aimed at identifying the most appropriate support for the siblings to help them cope better. The study followed the Resiliency Model of Family Stress, Adjustment, and Adaptation and a narrative theory approach. An in-depth interview with the parents was conducted for the study, so the findings reflect the parents' perception of the siblings. All the themes emerged into two categories: life in the family setting and supports. The findings indicate that the families are striving for balance between the siblings and the children with ASD, but still tend to focus more on the children with ASD. Also, the families tend to have autonomous personal support systems. The parents tend to perceive that these personal support systems are good enough for the siblings; therefore, the parents do not feel that formal support for the siblings was necessary. As a result of the findings, recommendations are made for the organizations that work with individuals with ASD to provide more appropriate services for the families of children with ASD, including siblings. Also, recommendations are made for future studies to clarify more factors related to the siblings due to the limitation of this study; the siblings' lives were reflected vicariously via the parents.
ContributorsJeong, Seong Hae (Author) / Marsiglia, Flavio F (Thesis advisor) / Ayers, Stephanie (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2013
Description
This report will review the mechanical and microstructural properties of the refractory element rhenium (Re) deposited using Laser Additive Manufacturing (LAM). With useable structural strength over 2200 °C, existing applications up to 2760 °C, very high strength, ductility and chemical resistance, interest in Re is understandable. This study includes data about tensile properties including tensile data up to 1925 °C, fracture modes, fatigue and microstructure including deformation systems and potential applications of that information. The bulk mechanical test data will be correlated with nanoindentation and crystallographic examination. LAM properties are compared to the existing properties found in the literature for other manufacturing processes. The literature indicates that Re has three significant slip systems but also twins as part of its deformation mechanisms. While it follows the hcp metal characteristics for deformation, it has interesting and valuable extremes such as high work hardening, potentially high strength, excellent wear resistance and superior elevated temperature strength. These characteristics are discussed in detail.
ContributorsAdams, Robbie (Author) / Chawla, Nikhilesh (Thesis advisor) / Adams, James (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2012
Description
In 2022, integrated circuit interconnects will approach 10 nm and the diffusion barrier layers needed to ensure long lasting devices will be at 1 nm. This dimension means the interconnect will be dominated by the interface and it has been shown the interface is currently eroding device performance. The standard interconnect system has three layers - a Copper metal core, a Tantalum Adhesion layer and a Tantalum Nitride Diffusion Barrier Layer. An alternate interconnect schema is a Tantalum Nitride barrier layer and Silver as a metal. The adhesion layer is removed from the system along with changing to an alternate, low resistivity metal. First principles are used to assess the interface of the Silver and Tantalum Nitride. Several stoichiometric 1:1 Tantalum Nitride polymorphs are assessed and it is found that the Fe2P crystal structure is actually the most stable crystal structure which is at odds with the published phase diagram for ambient crystal structure. The surface stability of Fe2P-TaN is assessed and the absorption enthalpy of Silver adatoms is calculated. Finally, the thermodynamic stability of the TaN-Ag interconnect system is assessed.
ContributorsGrumski, Michael (Author) / Adams, James (Thesis advisor) / Krause, Stephen (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2012
Description
As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.
ContributorsCavendish, Rio (Author) / Crozier, Peter (Thesis advisor) / Adams, James (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Cancer claims hundreds of thousands of lives every year in US alone. Finding ways for early detection of cancer onset is crucial for better management and treatment of cancer. Thus, biomarkers especially protein biomarkers, being the functional units which reflect dynamic physiological changes, need to be discovered. Though important, there are only a few approved protein cancer biomarkers till date. To accelerate this process, fast, comprehensive and affordable assays are required which can be applied to large population studies. For this, these assays should be able to comprehensively characterize and explore the molecular diversity of nominally "single" proteins across populations. This information is usually unavailable with commonly used immunoassays such as ELISA (enzyme linked immunosorbent assay) which either ignore protein microheterogeneity, or are confounded by it. To this end, mass spectrometric immuno assays (MSIA) for three different human plasma proteins have been developed. These proteins viz. IGF-1, hemopexin and tetranectin have been found in reported literature to show correlations with many diseases along with several carcinomas. Developed assays were used to extract entire proteins from plasma samples and subsequently analyzed on mass spectrometric platforms. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometric techniques where used due to their availability and suitability for the analysis. This resulted in visibility of different structural forms of these proteins showing their structural micro-heterogeneity which is invisible to commonly used immunoassays. These assays are fast, comprehensive and can be applied in large sample studies to analyze proteins for biomarker discovery.
ContributorsRai, Samita (Author) / Nelson, Randall (Thesis advisor) / Hayes, Mark (Thesis advisor) / Borges, Chad (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2012
Description
The transition to lead-free solder in the electronics industry has benefitted the environment in many ways. However, with new materials systems comes new materials issues. During the processing of copper pads, a protective surface treatment is needed to prevent the copper from oxidizing. Characterizing the copper oxidation underneath the surface treatment is challenging but necessary for product reliability and failure analysis. Currently, FIB-SEM, which is time-consuming and expensive, is what is used to understand and analyze the surface treatment-copper oxide(s)-copper system. This project's goals were to determine a characterization methodology that cuts both characterization time and cost in half for characterizing copper oxidation beneath a surface treatment and to determine which protective surface treatment is the best as defined by multiple criterion such as cost, sustainability, and reliability. Two protective surface treatments, organic solderability preservative (OSP) and chromium zincate, were investigated, and multiple characterization techniques were researched. Six techniques were tested, and three were deemed promising. Through our studies, it was determined that the best surface treatment was organic solderability preservative (OSP) and the ideal characterization methodology would be using FIB-SEM to calibrate a QCM model, along with using SERA to confirm the QCM model results. The methodology we propose would result in a 91% reduction in characterization cost and a 92% reduction in characterization time. Future work includes further calibration of the QCM model using more FIB/SEM data points and eventually creating a model for oxide layer thickness as a function of exposure time and processing temperature using QCM as the primary data source. In doing my Capstone project for Intel, a large electronics manufacturing company, I feel it is important to remember the effects of our tools and industry on the environment and to consider the product life cycle in terms other than monetary gain and raw material recycling. To this end I will be discussing how lead is and was used in manufacturing, how it is disposed of, and how this effects the environment including plant, animal, and insect life, as well as ground water contamination. Since the ban was enacted several years ago, I will compare how lead-free alternatives currently in use compare in environmental impact and possibly raise the question of whether we have simply traded one evil for another.
ContributorsBranch Kelly, Marion Zoe (Author) / Adams, James (Thesis director) / Krause, Stephen (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2015-05