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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
Aluminum alloys and their composites are attractive materials for applications requiring high strength-to-weight ratios and reasonable cost. Many of these applications, such as those in the aerospace industry, undergo fatigue loading. An understanding of the microstructural damage that occurs in these materials is critical in assessing their fatigue resistance. Two

Aluminum alloys and their composites are attractive materials for applications requiring high strength-to-weight ratios and reasonable cost. Many of these applications, such as those in the aerospace industry, undergo fatigue loading. An understanding of the microstructural damage that occurs in these materials is critical in assessing their fatigue resistance. Two distinct experimental studies were performed to further the understanding of fatigue damage mechanisms in aluminum alloys and their composites, specifically fracture and plasticity. Fatigue resistance of metal matrix composites (MMCs) depends on many aspects of composite microstructure. Fatigue crack growth behavior is particularly dependent on the reinforcement characteristics and matrix microstructure. The goal of this work was to obtain a fundamental understanding of fatigue crack growth behavior in SiC particle-reinforced 2080 Al alloy composites. In situ X-ray synchrotron tomography was performed on two samples at low (R=0.1) and at high (R=0.6) R-ratios. The resulting reconstructed images were used to obtain three-dimensional (3D) rendering of the particles and fatigue crack. Behaviors of the particles and crack, as well as their interaction, were analyzed and quantified. Four-dimensional (4D) visual representations were constructed to aid in the overall understanding of damage evolution. During fatigue crack growth in ductile materials, a plastic zone is created in the region surrounding the crack tip. Knowledge of the plastic zone is important for the understanding of fatigue crack formation as well as subsequent growth behavior. The goal of this work was to quantify the 3D size and shape of the plastic zone in 7075 Al alloys. X-ray synchrotron tomography and Laue microdiffraction were used to non-destructively characterize the volume surrounding a fatigue crack tip. The precise 3D crack profile was segmented from the reconstructed tomography data. Depth-resolved Laue patterns were obtained using differential-aperture X-ray structural microscopy (DAXM), from which peak-broadening characteristics were quantified. Plasticity, as determined by the broadening of diffracted peaks, was mapped in 3D. Two-dimensional (2D) maps of plasticity were directly compared to the corresponding tomography slices. A 3D representation of the plastic zone surrounding the fatigue crack was generated by superimposing the mapped plasticity on the 3D crack profile.
ContributorsHruby, Peter (Author) / Chawla, Nikhilesh (Thesis advisor) / Solanki, Kiran (Committee member) / Liu, Yongming (Committee member) / Arizona State University (Publisher)
Created2014
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Description
In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles

In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications.
ContributorsMa, Teng (Author) / Jiang, Hanqing (Thesis advisor) / Yu, Hongyu (Committee member) / Yu, Hongbin (Committee member) / Poon, Poh Chieh Benny (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2014
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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
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Description
Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency

Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases.

In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated.

Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a microcavity organic light emitting diode (MOLED), significant enhancement in the external quantum efficiency was achieved. The optimized MOLED structure achieved a light out-coupling enhancement of 1.35 compared to the non-cavity structure with a peak EQE of 34.2%. In addition to demonstrating a high light out-coupling enhancement, the microcavity effect of a narrow band emitter in a MOLED was elucidated.
ContributorsEcton, Jeremy David (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Concrete is the most widely used infrastructure material worldwide. Production of portland cement, the main binding component in concrete, has been shown to require significant energy and account for approximately 5-7% of global carbon dioxide production. The expected continued increased use of concrete over the coming decades indicates this is

Concrete is the most widely used infrastructure material worldwide. Production of portland cement, the main binding component in concrete, has been shown to require significant energy and account for approximately 5-7% of global carbon dioxide production. The expected continued increased use of concrete over the coming decades indicates this is an ideal time to implement sustainable binder technologies. The current work aims to explore enhanced sustainability concretes, primarily in the context of limestone and flow. Aspects such as hydration kinetics, hydration product formation and pore structure add to the understanding of the strength development and potential durability characteristics of these binder systems. Two main strategies for enhancing this sustainability are explored in this work: (i) the use of high volume limestone in combination with other alternative cementitious materials to decrease the portland cement quantity in concrete and (ii) the use of geopolymers as the binder phase in concrete. The first phase of the work investigates the use of fine limestone as cement replacement from the perspective of hydration, strength development, and pore structure. The nature of the potential synergistic benefit of limestone and alumina will be explored. The second phase will focus on the rheological characterization of these materials in the fresh state, as well as a more general investigation of the rheological characterization of suspensions. The results of this work indicate several key ideas. (i) There is a potential synergistic benefit for strength, hydration, and pore structure by using alumina and in portland limestone cements, (ii) the limestone in these systems is shown to react to some extent, and fine limestone is shown to accelerate hydration, (iii) rheological characteristics of cementitious suspensions are complex, and strongly dependent on several key parameters including: the solid loading, interparticle forces, surface area of the particles present, particle size distribution of the particles, and rheological nature of the media in which the particles are suspended, and (iv) stress plateau method is proposed for the determination of rheological properties of concentrated suspensions, as it more accurately predicts apparent yield stress and is shown to correlate well with other viscoelastic properties of the suspensions.
ContributorsVance, Kirk (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Chawla, Nikhilesh (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of

Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl components in the ligand. These complexes possess interesting luminescent properties including ultra-narrow emission and metal assisted delayed fluorescence (MADF) emission.
ContributorsTurner, Eric (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2014
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Description
For decades, microelectronics manufacturing has been concerned with failures related to electromigration phenomena in conductors experiencing high current densities. The influence of interconnect microstructure on device failures related to electromigration in BGA and flip chip solder interconnects has become a significant interest with reduced individual solder interconnect volumes. A survey

For decades, microelectronics manufacturing has been concerned with failures related to electromigration phenomena in conductors experiencing high current densities. The influence of interconnect microstructure on device failures related to electromigration in BGA and flip chip solder interconnects has become a significant interest with reduced individual solder interconnect volumes. A survey indicates that x-ray computed micro-tomography (µXCT) is an emerging, novel means for characterizing the microstructures' role in governing electromigration failures. This work details the design and construction of a lab-scale µXCT system to characterize electromigration in the Sn-0.7Cu lead-free solder system by leveraging in situ imaging.

In order to enhance the attenuation contrast observed in multi-phase material systems, a modeling approach has been developed to predict settings for the controllable imaging parameters which yield relatively high detection rates over the range of x-ray energies for which maximum attenuation contrast is expected in the polychromatic x-ray imaging system. In order to develop this predictive tool, a model has been constructed for the Bremsstrahlung spectrum of an x-ray tube, and calculations for the detector's efficiency over the relevant range of x-ray energies have been made, and the product of emitted and detected spectra has been used to calculate the effective x-ray imaging spectrum. An approach has also been established for filtering `zinger' noise in x-ray radiographs, which has proven problematic at high x-ray energies used for solder imaging. The performance of this filter has been compared with a known existing method and the results indicate a significant increase in the accuracy of zinger filtered radiographs.

The obtained results indicate the conception of a powerful means for the study of failure causing processes in solder systems used as interconnects in microelectronic packaging devices. These results include the volumetric quantification of parameters which are indicative of both electromigration tolerance of solders and the dominant mechanisms for atomic migration in response to current stressing. This work is aimed to further the community's understanding of failure-causing electromigration processes in industrially relevant material systems for microelectronic interconnect applications and to advance the capability of available characterization techniques for their interrogation.
ContributorsMertens, James Charles Edwin (Author) / Chawla, Nikhilesh (Thesis advisor) / Alford, Terry (Committee member) / Jiao, Yang (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Commercially pure (CP) and extra low interstitial (ELI) grade Ti-alloys present excellent corrosion resistance, lightweight, and formability making them attractive materials for expanded use in transportation and medical applications. However, the strength and toughness of CP titanium are affected by relatively small variations in their impurity/solute content (IC), e.g., O,

Commercially pure (CP) and extra low interstitial (ELI) grade Ti-alloys present excellent corrosion resistance, lightweight, and formability making them attractive materials for expanded use in transportation and medical applications. However, the strength and toughness of CP titanium are affected by relatively small variations in their impurity/solute content (IC), e.g., O, Al, and V. This increase in strength is due to the fact that the solute either increases the critical stress required for the prismatic slip systems ({10-10}<1-210>) or activates another slip system ((0001)<11-20>, {10-11}<11-20>). In particular, solute additions such as O can effectively strengthen the alloy but with an attendant loss in ductility by changing the behavior from wavy (cross slip) to planar nature. In order to understand the underlying behavior of strengthening by solutes, it is important to understand the atomic scale mechanism. This dissertation aims to address this knowledge gap through a synergistic combination of density functional theory (DFT) and molecular dynamics. Further, due to the long-range strain fields of the dislocations and the periodicity of the DFT simulation cells, it is difficult to apply ab initio simulations to study the dislocation core structure. To alleviate this issue we developed a multiscale quantum mechanics/molecular mechanics approach (QM/MM) to study the dislocation core. We use the developed QM/MM method to study the pipe diffusion along a prismatic edge dislocation core. Complementary to the atomistic simulations, the Semi-discrete Variational Peierls-Nabarro model (SVPN) was also used to analyze the dislocation core structure and mobility. The chemical interaction between the solute/impurity and the dislocation core is captured by the so-called generalized stacking fault energy (GSFE) surface which was determined from DFT-VASP calculations. By taking the chemical interaction into consideration the SVPN model can predict the dislocation core structure and mobility in the presence and absence of the solute/impurity and thus reveal the effect of impurity/solute on the softening/hardening behavior in alpha-Ti. Finally, to study the interaction of the dislocation core with other planar defects such as grain boundaries (GB), we develop an automated method to theoretically generate GBs in HCP type materials.
ContributorsBhatia, Mehul Anoopkumar (Author) / Solanki, Kiran N (Thesis advisor) / Peralta, Pedro (Committee member) / Jiang, Hanqing (Committee member) / Neithalath, Narayanan (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The United States Department of Energy (DOE) has always held the safety and reliability of the nation's nuclear reactor fleet as a top priority. Continual improvements and advancements in nuclear fuels have been instrumental in maximizing energy generation from nuclear power plants and minimizing waste. One aspect of the DOE

The United States Department of Energy (DOE) has always held the safety and reliability of the nation's nuclear reactor fleet as a top priority. Continual improvements and advancements in nuclear fuels have been instrumental in maximizing energy generation from nuclear power plants and minimizing waste. One aspect of the DOE Fuel Cycle Research and Development Advanced Fuels Campaign is to improve the mechanical properties of uranium dioxide (UO2) for nuclear fuel applications.

In an effort to improve the performance of UO2, by increasing the fracture toughness and ductility, small quantities of oxide materials have been added to samples to act as dopants. The different dopants used in this study are: titanium dioxide, yttrium oxide, aluminum oxide, silicon dioxide, and chromium oxide. The effects of the individual dopants and some dopant combinations on the microstructure and mechanical properties are determined using indentation fracture experiments in tandem with scanning electron microscopy. Indentation fracture experiments are carried out at room temperature and at temperatures between 450 °C and 1160 °C.

The results of this work find that doping with aluminosilicate produces the largest favorable change in the mechanical properties of UO2. This sample exhibits an increase in fracture toughness at room temperature without showing a change in yield strength at elevated temperatures. The results also show that doping with Al2O3 and TiO2 produce stronger samples and it is hypothesized that this is a result of the sample containing dopant-rich secondary phase particles.
ContributorsMcDonald, Robert (Author) / Peralta, Pedro (Thesis advisor) / Rajagopalan, Jagannathan (Committee member) / Solanki, Kiran (Committee member) / Arizona State University (Publisher)
Created2014