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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

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
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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,

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
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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

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
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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

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
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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

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
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Description
Organic materials have emerged as an attractive component of electronics over the past few decades, particularly in the development of efficient and stable organic light-emitting diodes (OLEDs) and organic neuromorphic devices. The electrical, chemical, physical, and optical studies of organic materials and their corresponding devices have been conducted for efficient

Organic materials have emerged as an attractive component of electronics over the past few decades, particularly in the development of efficient and stable organic light-emitting diodes (OLEDs) and organic neuromorphic devices. The electrical, chemical, physical, and optical studies of organic materials and their corresponding devices have been conducted for efficient and stable electronics. The development of efficient and stable deep blue OLED devices remains a challenge that has obstructed the progress of large-scale OLED commercialization. One approach was taken to achieve a deep blue emitter through a color tuning strategy. A new complex, PtNONS56-dtb, was designed and synthesized by controlling the energy gap between T1 and T2 energy states to achieve narrowed and blueshifted emission spectra. This emitter material showed an emission spectrum at 460 nm with a FWHM of 59 nm at room temperature in PMMA, and the PtNONS56-dtb-based device exhibited a peak EQE of 8.5% with CIE coordinates of (0.14, 0.27). A newly developed host and electron blocking materials were demonstrated to achieve efficient and stable OLED devices. The indolocarbazole-based materials were designed to have good hole mobility and high triplet energy. BCN34 as an electron blocking material achieved the estimated LT80 of 12509 h at 1000 cd m-2 with a peak EQE of 30.3% in devices employing Pd3O3 emitter. Additionally, a device with bi-layer emissive layer structure, using BCN34 and CBP as host materials doped with PtN3N emitter, achieved a peak EQE of 16.5% with the LT97 of 351 h at 1000 cd m-2. A new neuromorphic device using Ru(bpy)3(PF6)2 as an active layer was designed to emulate the short-term characteristics of a biological synapse. This memristive device showed a similar operational mechanism with biological synapse through the movement of ions and electronic charges. Furthermore, the performance of the device showed tunability by adding salt. Ultimately, the device with 2% LiClO4 salt shows similar timescales to short-term plasticity characteristics of biological synapses.
ContributorsShin, Samuel (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Over the past three decades, significant progress in the development of organic light-emitting diodes (OLEDs) has been achieved, enabling OLEDs to become a main component in state-of-the-art displays and next generation solid-state lighting. As this technology advances, it is highly desirable to further improve the device efficiency and operational stability

Over the past three decades, significant progress in the development of organic light-emitting diodes (OLEDs) has been achieved, enabling OLEDs to become a main component in state-of-the-art displays and next generation solid-state lighting. As this technology advances, it is highly desirable to further improve the device efficiency and operational stability to drive the success of OLEDs in future display and lighting applications. This dissertation aims at developing novel organic emitting materials covering visible and near-infrared (NIR) emissions for efficient and table OLEDs. Firstly, a series of tetradentate Pd(II) complexes, which have attractive phosphorescent aggregate emission performance especially at high brightness level in device settings, have been developed. The luminescent lifetime of Pd(II) complex aggregates was demonstrated to be shorter than 1 μs with a close-to-unity photoluminescence quantum yield. Moreover, a systematic study regarding structure-property relationship was conducted on four tetradentate Pd(II) complexes, i.e., Pd3O3, Pd3O8-P, Pd3O8-Py2, and Pd3O8-Py5, featuring aggregate emission. As a result, an extremely efficient and stable OLED device utilizing Pd3O8-Py5 was achieved. It demonstrated a peak external quantum efficiency (EQE) of 37.3% with a reduced efficiency roll-off retaining a high EQE of 32.5% at 10000 cd m-2, and an estimated LT95 lifetime (time to 95% of the initial luminance) of 48246 h at 1000 cd m-2. Secondly, there is an increasing demand for NIR OLEDs with emission spectra beyond 900 nm to expand their applications in biometric authentication, night vision display, and telecommunication, etc. A stable and efficient NIR Pt(II) porphyrin complex named PtTPTNP-F8 was developed, and exhibited an electroluminescent spectrum at 920 nm. By carefully choosing the host materials, an PtTPTNP-F8 based NIR OLED achieved a EQE of 1.9%. Furthermore, an PtTPTNP-F8 OLED fabricated in a stable device structure demonstrated extraordinary operational stability with LT99 of >1000 h at 20 mA cm-2. Lastly, a series of imidazole-based blue Pt(II) complexes were developed and studied. Results indicated that structural modification of ligand molecules effectively tuned the emission spectral wavelength and bandwidth. Two blue complexes, i.e., Pt2O2 P2M and Pt2O2-PPy5-M, emitting at 472 and 476 nm respectively, exhibited narrow-band emission spectra with a full width at half maximum of 16 nm.
ContributorsCao, Linyu (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Organic electronics have remained a research topic of great interest over the past few decades, with organic light emitting diodes (OLEDs) emerging as a disruptive technology for lighting and display applications. While OLED performance has improved significantly over the past decade, key issues remain unsolved such as the development of

Organic electronics have remained a research topic of great interest over the past few decades, with organic light emitting diodes (OLEDs) emerging as a disruptive technology for lighting and display applications. While OLED performance has improved significantly over the past decade, key issues remain unsolved such as the development of stable and efficient blue devices. In order to further the development of OLEDs and increase their commercial potential, innovative device architectures, novel emissive materials and high-energy hosts are designed and reported.

OLEDs employing step-wide graded-doped emissive layers were designed to improve charge balance and center the exciton formation zone leading to improved device performance. A red OLED with a peak efficiency of 16.9% and an estimated LT97 over 2,000 hours at 1,000 cd/m2 was achieved. Employing a similar structure, a sky-blue OLED was demonstrated with a peak efficiency of 17.4% and estimated LT70 over 1,300 hours at 1,000 cd/m2. Furthermore, the sky-blue OLEDs color was improved to CIE coordinates of (0.15, 0.25) while maintaining an efficiency of 16.9% and estimated LT70 over 600 hours by incorporating a fluorescent sensitizer. These devices represent literature records at the time of publication for efficient and stable platinum phosphorescent OLEDs.

A newly developed class of emitters, metal-assisted delayed-fluorescence (MADF), are demonstrated to achieve higher-energy emission from a relatively low triplet energy. A green MADF device reaches a peak efficiency of 22% with an estimated LT95 over 350 hours at 1,000 cd/m2. Additionally, a blue charge confined OLED of PtON1a-tBu demonstrated a peak efficiency above 20%, CIE coordinated of (0.16, 0.27), and emission onset at 425 nm.

High triplet energy hosts are required for the realization of stable and efficient deep blue emission. A rigid “M”-type carbazole/fluorene hybrid called mDCzPF and a carbazole/9-silafluorene hybrid called mDCzPSiF are demonstrated to have high triplet energies ET=2.88 eV and 3.03 eV respectively. Both hosts are demonstrated to have reasonable stability and can serve as a template for future material design. The techniques presented here demonstrate alternative approaches for improving the performance of OLED devices and help to bring this technology closer to widespread commercialization.
ContributorsKlimes, Kody George (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Wang, Liping (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Understanding the diversity, evolutionary relationships, and geographic distribution of species is foundational knowledge in biology. However, this knowledge is lacking for many diverse lineages of the tree of life. This is the case for the desert stink beetles in the tribe Amphidorini LeConte, 1862 (Coleoptera: Tenebrionidae) – a lineage of

Understanding the diversity, evolutionary relationships, and geographic distribution of species is foundational knowledge in biology. However, this knowledge is lacking for many diverse lineages of the tree of life. This is the case for the desert stink beetles in the tribe Amphidorini LeConte, 1862 (Coleoptera: Tenebrionidae) – a lineage of arid-adapted flightless beetles found throughout western North America. Four interconnected studies that jointly increase our knowledge of this group are presented. First, the darkling beetle fauna of the Algodones sand dunes in southern California is examined as a case study to explore the scientific practice of checklist creation. An updated list of the species known from this region is presented, with a critical focus on material now made available through digitization and global aggregation. This part concludes with recommendations for future biodiversity checklist authors. Second, the psammophilic genus Trogloderus LeConte, 1879 is revised. Six new species are described, and the first, multi-gene phylogeny for the genus is inferred. In addition, historical biogeographic reconstructions along with novel hypotheses of speciation patterns within the Intermountain Region are given. In particular, the Kaibab Plateau and Kaiparowitz Formation are found to have promoted speciation on the Colorado Plateau. The Owens Valley and prehistoric Bouse Embayment are similarly hypothesized to drive species diversification in southern California. Third, a novel phylogenomic analysis for the tribe Amphidorini is presented, based on 29 de novo partial transcriptomes. Three putative ortholog sets were discovered and analyzed to infer the relationships between species groups and genera. The existing classification of the tribe is found to be highly inadequate, though the earliest-diverging relationships within the tribe are still in question. Finally, the new phylogenetic framework is used to provide a genus-level revision for the Amphidorini, which previously contained six valid genera and 253 valid species. This updated classification includes more than 100 taxonomic changes and results in the revised tribe consisting of 16 genera, with three being described as new to science.
ContributorsJohnston, Murray Andrew (Author) / Franz, Nico M (Thesis advisor) / Cartwright, Reed (Committee member) / Taylor, Jesse (Committee member) / Pigg, Kathleen (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials,

Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, ∆EDA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt-16. Furthermore, the development of a series of tetradentate Pt complexes yielded highly efficient and stable single doped white devices due to their halogen free tetradentate design. In addition to these benchmark achievements, the systematic molecular modification of both emissive and absorbing materials provides valuable structure-property relationship information that should help guide further developments in the field.
ContributorsFleetham, Tyler Blain (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2014