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- Genre: Doctoral Dissertation
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
The Cape Floral Region (CFR) in southwestern South Africa is one of the most diverse in the world, with >9,000 plant species, 70% of which are endemic, in an area of only ~90,000 km2. Many have suggested that the CFR's heterogeneous environment, with respect to landscape gradients, vegetation, rainfall, elevation, and soil fertility, is responsible for the origin and maintenance of this biodiversity. While studies have struggled to link species diversity with these features, no study has attempted to associate patterns of gene flow with environmental data to determine how CFR biodiversity evolves on different scales. Here, a molecular population genetic data is presented for a widespread CFR plant, Leucadendron salignum, across 51 locations with 5-kb of chloroplast (cpDNA) and 6-kb of unlinked nuclear (nuDNA) DNA sequences in a dataset of 305 individuals. In the cpDNA dataset, significant genetic structure was found to vary on temporal and spatial scales, separating Western and Eastern Capes - the latter of which appears to be recently derived from the former - with the highest diversity in the heart of the CFR in a central region. A second study applied a statistical model using vegetation and soil composition and found fine-scale genetic divergence is better explained by this landscape resistance model than a geographic distance model. Finally, a third analysis contrasted cpDNA and nuDNA datasets, and revealed very little geographic structure in the latter, suggesting that seed and pollen dispersal can have different evolutionary genetic histories of gene flow on even small CFR scales. These three studies together caution that different genomic markers need to be considered when modeling the geographic and temporal origin of CFR groups. From a greater perspective, the results here are consistent with the hypothesis that landscape heterogeneity is one driving influence in limiting gene flow across the CFR that can lead to species diversity on fine-scales. Nonetheless, while this pattern may be true of the widespread L. salignum, the extension of this approach is now warranted for other CFR species with varying ranges and dispersal mechanisms to determine how universal these patterns of landscape genetic diversity are.
ContributorsTassone, Erica (Author) / Verrelli, Brian C (Thesis advisor) / Dowling, Thomas (Committee member) / Cartwright, Reed (Committee member) / Rosenberg, Michael S. (Committee member) / Wojciechowski, Martin (Committee member) / Arizona State University (Publisher)
Created2013
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
Contaminants of emerging concern (CECs) present in wastewater effluent can threat its safe discharge or reuse. Additional barriers of protection can be provided using advanced or natural treatment processes. This dissertation evaluated ozonation and constructed wetlands to remove CECs from wastewater effluent. Organic CECs can be removed by hydroxyl radical formed during ozonation, however estimating the ozone demand of wastewater effluent is complicated due to the presence of reduced inorganic species. A method was developed to estimate ozone consumption only by dissolved organic compounds and predict trace organic oxidation across multiple wastewater sources. Organic and engineered nanomaterial (ENM) CEC removal in constructed wetlands was investigated using batch experiments and continuous-flow microcosms containing decaying wetland plants. CEC removal varied depending on their physico-chemical properties, hydraulic residence time (HRT) and relative quantities of plant materials in the microcosms. At comparable HRTs, ENM removal improved with higher quantity of plant materials due to enhanced sorption which was verified in batch-scale studies with plant materials. A fate-predictive model was developed to evaluate the role of design loading rates on organic CEC removal. Areal removal rates increased with hydraulic loading rates (HLRs) and carbon loading rates (CLRs) unless photolysis was the dominant removal mechanism (e.g. atrazine). To optimize CEC removal, wetlands with different CLRs can be used in combination without lowering the net HLR. Organic CEC removal in denitrifying conditions of constructed wetlands was investigated and selected CECs (e.g. estradiol) were found to biotransform while denitrification occurred. Although level of denitrification was affected by HRT, similar impact on estradiol was not observed due to a dominant effect from plant biomass quantity. Overall, both modeling and experimental findings suggest considering CLR as an equally important factor with HRT or HLR to design constructed wetlands for CEC removal. This dissertation provided directions to select design parameters for ozonation (ozone dose) and constructed wetlands (design loading rates) to meet organic CEC removal goals. Future research is needed to understand fate of ENMs during ozonation and quantify the contributions from different transformation mechanisms occurring in the wetlands to incorporate in a model and evaluate the effect of wetland design.
ContributorsSharif, Fariya (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Fox, Peter (Committee member) / Herckes, Pierre (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
The overall goal of this dissertation is to advance understanding of biofilm reduction of oxidized contaminants in water and wastewater. Chapter 1 introduces the fundamentals of biological reduction of three oxidized contaminants (nitrate, perchlorate, and trichloriethene (TCE)) using two biofilm processes (hydrogen-based membrane biofilm reactors (MBfR) and packed-bed heterotrophic reactors (PBHR)), and it identifies the research objectives. Chapters 2 through 6 focus on nitrate removal using the MBfR and PBHR, while chapters 7 through 10 investigate simultaneous reduction of nitrate and another oxidized compound (perchlorate, sulfate, or TCE) in the MBfR. Chapter 11 summarizes the major findings of this research. Chapters 2 and 3 demonstrate nitrate removal in a groundwater and identify the maximum nitrate loadings using a pilot-scale MBfR and a pilot-scale PBHR, respectively. Chapter 4 compares the MBfR and the PBHR for denitrification of the same nitrate-contaminated groundwater. The comparison includes the maximum nitrate loading, the effluent water quality of the denitrification reactors, and the impact of post-treatment on water quality. Chapter 5 theoretically and experimentally demonstrates that the nitrate biomass-carrier surface loading, rather than the traditionally used empty bed contact time or nitrate volumetric loading, is the primary design parameter for heterotrophic denitrification. Chapter 6 constructs a pH-control model to predict pH, alkalinity, and precipitation potential in heterotrophic or hydrogen-based autotrophic denitrification reactors. Chapter 7 develops and uses steady-state permeation tests and a mathematical model to determine the hydrogen-permeation coefficients of three fibers commonly used in the MBfR. The coefficients are then used as inputs for the three models in Chapters 8-10. Chapter 8 develops a multispecies biofilm model for simultaneous reduction of nitrate and perchlorate in the MBfR. The model quantitatively and systematically explains how operating conditions affect nitrate and perchlorate reduction and biomass distribution via four mechanisms. Chapter 9 modifies the nitrate and perchlorate model into a nitrate and sulfate model and uses it to identify operating conditions corresponding to onset of sulfate reduction. Chapter 10 modifies the nitrate and perchlorate model into a nitrate and TCE model and uses it to investigate how operating conditions affect TCE reduction and accumulation of TCE reduction intermediates.
ContributorsTang, Youneng (Author) / Rittmann, Bruce E. (Thesis advisor) / Westerhoff, Paul (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Halden, Rolf (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
The objective of this research was to predict the persistence of potential future contaminants in indirect potable reuse systems. In order to accurately estimate the fates of future contaminants in indirect potable reuse systems, results describing persistence from EPI Suite were modified to include sorption and oxidation. The target future contaminants studied were the approximately 2000 pharmaceuticals currently undergoing testing by United States Food and Drug Administration (US FDA). Specific organic substances such as analgesics, antibiotics, and pesticides were used to verify the predicted half-lives by comparing with reported values in the literature. During sub-surface transport, an important component of indirect potable reuse systems, the effects of sorption and oxidation are important mechanisms. These mechanisms are not considered by the quantitative structure activity relationship (QSAR) model predictions for half-lives from EPI Suite. Modifying the predictions from EPI Suite to include the effects of sorption and oxidation greatly improved the accuracy of predictions in the sub-surface environment. During validation, the error was reduced by over 50% when the predictions were modified to include sorption and oxidation. Molecular weight (MW) is an important criteria for estimating the persistence of chemicals in the sub-surface environment. EPI Suite predicts that high MW compounds are persistent since the QSAR model assumes steric hindrances will prevent transformations. Therefore, results from EPI Suite can be very misleading for high MW compounds. Persistence was affected by the total number of halogen atoms in chemicals more than the sum of N-heterocyclic aromatics in chemicals. Most contaminants (over 90%) were non-persistent in the sub-surface environment suggesting that the target future drugs do not pose a significant risk to potable reuse systems. Another important finding is that the percentage of compounds produced from the biotechnology industry is increasing rapidly and should dominate the future production of pharmaceuticals. In turn, pharmaceuticals should become less persistent in the future. An evaluation of indirect potable reuse systems that use reverse osmosis (RO) for potential rejection of the target contaminants was performed by statistical analysis. Most target compounds (over 95%) can be removed by RO based on size rejection and other removal mechanisms.
ContributorsLim, Seung (Author) / Fox, Peter (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2011
Description
Organic light-emitting diodes (OLEDs) have been successfully implemented in various display applications owing to rapid advancements in material design and device architecture. Their success in the display industry has ignited a rising interest in applying OLEDs for solid-state lighting applications through the development of white OLEDs (WOLEDs). However, to enter the market as a serious competitor, WOLEDs must achieve excellent color quality, high external quantum efficiency (EQE) as well as a long operational lifetime. In this research, novel materials and device architectures were explored to improve the performance of single-stack WOLEDs. A new Pt-based phosphorescent emitter, Pt2O2-p2m, was examined as a single emissive emitter for the development of a stable and efficient single-doped WOLED. A bilayer structure was employed to balance the charges carriers within the emissive layer resulting in low efficiency roll-off at high brightness, realizing a peak EQE of 21.5% and EQEs of 20% at 1000 cd m-2 and 15.3% at 7592 cd m-2. A novel phosphorescent/fluorescent, or hybrid, WOLED device architecture was also proposed. To gather a thorough understanding of blue fluorescent OLEDs prior to its use in a WOLED, a study was conducted to investigate the impact of the material selection on the device performance. The use of an anthracene type host demonstrated an improvement to the operational stability of the blue OLED by reducing the occurrence of degradation events. Additionally, various dopant concentrations and blocking materials revealed vastly different efficiency and lifetime results. Finally, a Pd (II) complex, Pd3O8-Py5, with efficient amber-colored aggregate emission was employed to produce a WOLED. Various host materials were investigated to achieve balanced white emission and the addition of an interlayer composed of a high triplet energy material was used to reduce quenching effects. Through this strategy, a color stable WOLED device with a peak EQE of 45% and an estimated LT95 over 50,000 hours at 1000 cd m-2 was realized. The comprehensive performance of the proposed device architecture competes with WOLED devices that are commercially available and reported within the literature domain, providing a strong foundation to further advance the development of highly efficient and stable single-stack WOLEDs.
ContributorsAmeri, Lydia (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2022
Description
The imaging and detection of specific cell types deep in biological tissue is critical for the diagnosis of cancer and the study of biological phenomena. Current high-resolution optical imaging techniques are depth limited due to the high degree of optical scattering that occurs in tissues. To address these limitations, photoacoustic (PA) techniques have emerged as noninvasive methods for the imaging and detection of specific biological structures at extended depths in vivo. In addition, near-infrared (NIR) contrast agents have further increased the depth at which PA imaging can be achieved in biological tissues. The goal of this research is to combine novel PA imaging and NIR labeling strategies for the diagnosis of disease and for the detection of neuronal subtypes. Central Hypothesis: Utilizing custom-designed PA systems and NIR labeling techniques will enable the detection of specific cell types in vitro and in mammalian brain slices. Work presented in this dissertation addresses the following: (Chapter 2): The custom photoacoustic flow cytometry system combined with NIR absorbing copper sulfide nanoparticles for the detection of ovarian circulating tumor cells (CTCs) at physiologically relevant concentrations. Results obtained from this Chapter provide a unique tool for the future detection of ovarian CTCs in patient samples at the point of care. (Chapter 3): The custom photoacoustic microscopy (PAM) system can detect genetically encoded near-infrared fluorescent proteins (iRFPs) in cells in vitro. Results obtained from this Chapter can significantly increase the depth at which neurons and cellular processes can be targeted and imaged in vitro. (Chapter 4): Utilizing the Cre/lox recombination system with AAV vectors will enable selective tagging of dopaminergic neurons with iRFP for detection in brain slices using PAM. Thus, providing a new means of increasing the depth at which neuronal subtypes can be imaged and detected in the mammalian brain. Significance: Knowledge gained from this research could have significant impacts on the PA detection of ovarian cancer and extend the depth at which neuronal subtypes are imaged in the mammalian brain.
ContributorsLusk, Joel F. (Author) / Smith, Barbara S. (Thesis advisor) / Halden, Rolf (Committee member) / Anderson, Trent (Committee member) / Arizona State University (Publisher)
Created2022