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Electromigration (EM) has been a serious reliability concern in microelectronics packaging for close to half a century now. Whenever the challenges of EM are overcome newer complications arise such as the demand for better performance due to increased miniaturization of semiconductor devices or the problems faced due to undesirable properties

Electromigration (EM) has been a serious reliability concern in microelectronics packaging for close to half a century now. Whenever the challenges of EM are overcome newer complications arise such as the demand for better performance due to increased miniaturization of semiconductor devices or the problems faced due to undesirable properties of lead-free solders. The motivation for the work is that there exists no fully computational modeling study on EM damage in lead-free solders (and also in lead-based solders). Modeling techniques such as one developed here can give new insights on effects of different grain features and offer high flexibility in varying parameters and study the corresponding effects. In this work, a new computational approach has been developed to study void nucleation and initial void growth in solders due to metal atom diffusion. It involves the creation of a 3D stochastic mesoscale model of the microstructure of a polycrystalline Tin structure. The next step was to identify regions of current crowding or ‘hot-spots’. This was done through solving a finite difference scheme on top of the 3D structure. The nucleation of voids due to atomic diffusion from the regions of current crowding was modeled by diffusion from the identified hot-spot through a rejection free kinetic Monte-Carlo scheme. This resulted in the net movement of atoms from the cathode to the anode. The above steps of identifying the hotspot and diffusing the atoms at the hot-spot were repeated and this lead to the initial growth of the void. This procedure was studied varying different grain parameters. In the future, the goal is to explore the effect of more grain parameters and consider other mechanisms of failure such as the formation of intermetallic compounds due to interstitial diffusion and dissolution of underbump metallurgy.
ContributorsKarunakaran, Deepak (Thesis advisor) / Jiao, Yang (Committee member) / Chawla, Nikhilesh (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2016
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Description
There is a fundamental attractiveness about harnessing renewable energy in an age when sustainability is an ethical norm. Lithium ion batteries and hydrogen fuels are considered the most promising energy source instead of fossil fuels. This work describes the investigation of new cathode materials and devices architectures for lithium ion

There is a fundamental attractiveness about harnessing renewable energy in an age when sustainability is an ethical norm. Lithium ion batteries and hydrogen fuels are considered the most promising energy source instead of fossil fuels. This work describes the investigation of new cathode materials and devices architectures for lithium ion batteries, and photocatalysts for their usage in water splitting and waste water treatment.

LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks.

Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting.

Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties.

Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions.
ContributorsCheng, Qian (Author) / Chan, Candace Kay (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016
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Description
Nanolaminate composite materials consist of alternating layers of materials at the nanoscale (≤100 nm). Due to the nanometer scale thickness of their layers, these materials display unique and tailorable properties. This enables us to alter both mechanical attributes such as strength and wear properties, as well as functional characteristics such

Nanolaminate composite materials consist of alternating layers of materials at the nanoscale (≤100 nm). Due to the nanometer scale thickness of their layers, these materials display unique and tailorable properties. This enables us to alter both mechanical attributes such as strength and wear properties, as well as functional characteristics such as biocompatibility, optical, and electronic properties. This dissertation focuses on understanding the mechanical behavior of the Al-SiC system. From a practical perspective, these materials exhibit a combination of high toughness and strength which is attractive for many applications. Scientifically, these materials are interesting due to the large elastic modulus mismatch between the layers. This, paired with the small layer thickness, allows a unique opportunity for scientists to study the plastic deformation of metals under extreme amounts of constraint.

Previous studies are limited in scope and a more diverse range of mechanical characterization is required to understand both the advantages and limitations of these materials. One of the major challenges with testing these materials is that they are only able to be made in thicknesses on the order of micrometers so the testing methods are limited to small volume techniques. This work makes use of both microscale testing techniques from the literature as well as novel methodologies. Using these techniques we are able to gain insight into aspects of the material’s mechanical behavior such as the effects of layer orientation, flaw dependent fracture, tension-compression asymmetry, fracture toughness as a function of layer thickness, and shear behavior as a function of layer thickness.
ContributorsMayer, Carl Randolph (Author) / Chawla, Nikhilesh (Thesis advisor) / Jiang, Hanqing (Committee member) / Molina-Aldareguia, Jon (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2016
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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
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
This research examines several critical aspects of the so-called "film induced cleavage" model of stress corrosion cracking using silver-gold alloys as the parent-phase material. The model hypothesizes that the corrosion generates a brittle nanoporous film, which subsequently fractures forming a high-speed crack that is injected into the uncorroded parent-phase alloy.

This research examines several critical aspects of the so-called "film induced cleavage" model of stress corrosion cracking using silver-gold alloys as the parent-phase material. The model hypothesizes that the corrosion generates a brittle nanoporous film, which subsequently fractures forming a high-speed crack that is injected into the uncorroded parent-phase alloy. This high speed crack owing to its kinetic energy can penetrate beyond the corroded layer into the parent phase and thus effectively reducing strength of the parent phase. Silver-gold alloys provide an ideal system to study this effect, as hydrogen effect can be ruled out on thermodynamic basis. During corrosion of the silver-gold alloy, the less noble metal i.e. silver is removed from the system leaving behind a nanoporous gold (NPG) layer. In the case of polycrystalline material, this corrosion process proceeds deeper along the grain boundary than the matrix grain. All of the cracks with apparent penetration beyond the corroded (dealloyed) layer are intergranular. Our aim was to study the crack penetration depth along the grain boundary to ascertain whether the penetration occurs past the grain-boundary dealloyed depth. EDS and imaging in high-resolution aberration corrected scanning transmission electron microscope (STEM) and atom probe tomography (APT) have been used to evaluate the grain boundary corrosion depth.

The mechanical properties of monolithic NPG are also studied. The motivation behind this is two-fold. The crack injection depth depends on the speed of the crack formed in the nanoporous layer, which in turn depends on the mechanical properties of the NPG. Also NPG has potential applications in actuation, sensing and catalysis. The measured value of the Young's modulus of NPG with 40 nm ligament size and 28% density was ~ 2.5 GPa and the Poisson's ratio was ~ 0.20. The fracture stress was observed to be ~ 11-13 MPa. There was no significant change observed between these mechanical properties on oxidation of NPG at 1.4 V. The fracture toughness value for the NPG was ~ 10 J/m2. Also dynamic fracture tests showed that the NPG is capable of supporting crack velocities ~ 100 - 180 m/s.
ContributorsBadwe, Nilesh (Author) / Sieradzki, Karl (Thesis advisor) / Peralta, Pedro (Committee member) / Oswald, Jay (Committee member) / Mahajan, Ravi (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
Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material

Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material design and introducing conductive polymer binders that serve as matrix of the active material in anode. This thesis aims for developing a novel method for preparing the anode to improve the capacity retention rate. This would require the anode to have high electrical conductivity, high ionic conductivity, and good mechanical properties, especially elasticity. Here the incorporation of a conducting polymer and a conductive hydrogel in Sn-based anodes using a one-step electrochemical deposition via a 3-electrode cell method is reported: the Sn particles and conductive component can be electrochemically synthesized and simultaneously deposited into a hybrid thin film onto the working electrode directly forming the anode. A well-defined three dimensional network structure consisting of Sn nanoparticles coated by conducting polymers is achieved. Such a conductive polymer-hydrogel network has multiple advantageous features: meshporous polymeric structure can offer the pathway for lithium ion transfer between the anode and electrolyte; the continuous electrically conductive polypyrrole network, with the electrostatic interaction with elastic, porous hydrogel, poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (PAMPS) as both the crosslinker and doping anion for polypyrrole (PPy) can decrease the volume expansion by creating porous scaffold and softening the system itself. Furthermore, by increasing the amount of PAMPS and creating an interval can improve the cycling performance, resulting in improved capacity retention about 80% after 20 cycles, compared with only 54% of that of the control sample without PAMPS. The cycle is performed under current of 0.1 C.
ContributorsGao, Tianxiang (Author) / He, Ximin (Thesis advisor) / Sieradzki, Karl (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Shock loading is a complex phenomenon that can lead to failure mechanisms such as strain localization, void nucleation and growth, and eventually spall fracture. The length scale of damage with respect to that of the surrounding microstructure has proven to be a key aspect in determining sites of failure initiation.

Shock loading is a complex phenomenon that can lead to failure mechanisms such as strain localization, void nucleation and growth, and eventually spall fracture. The length scale of damage with respect to that of the surrounding microstructure has proven to be a key aspect in determining sites of failure initiation. Studying incipient stages of spall damage is of paramount importance to accurately determine initiation sites in the material microstructure where damage will nucleate and grow and to formulate continuum models that account for the variability of the damage process due to microstructural heterogeneity, which is the focus of this research. Shock loading experiments were conducted via flyer-plate impact tests for pressures of 2-6 GPa and strain rates of 105/s on copper polycrystals of varying thermomechanical processing conditions. Serial cross sectioning of recovered target disks was performed along with electron microscopy, electron backscattering diffraction (EBSD), focused ion beam (FIB) milling, and 3-D X-ray tomogrpahy (XRT) to gain 2-D and 3-D information on the spall plane and surrounding microstructure. Statistics on grain boundaries (GB) containing damage were obtained from 2-D data and GBs of misorientations 25° and 50° were found to have the highest probability to contain damage in as-received (AR), heat treated (HT), and fully recrystallized (FR) microstructures, while {111} Σ3 GBs were globally strong. The AR microstructure’s probability peak was the most pronounced indicating GB strength is the dominant factor for damage nucleation. 3-D XRT data was used to digitally render the spall planes of the AR, HT, and FR microstructures. From shape fitting the voids to ellipsoids, it was found that the AR microstructure contained greater than 55% intergranular damage, whereas the HT and FR microstructures contained predominantly transgranular and coalesced damage modes, respectively. 3-D reconstructions of large volume damage sites in shocked Cu multicrystals showed preference for damage nucleation at GBs between adjacent grains of a high Taylor factor mismatches as well as an angle between the shock direction and the GB physical normal of ~30°-45°. 3-D FIB sectioning of individual voids led to the discovery of uniform plastic zones ~25-50% the size of the void diameter and plastic deformation directions were characterized via local average misorientation maps. Incipient transgranular voids revealed from the sectioning process were present in grains of high Taylor factors along the shock direction, which is expected as materials with a low Taylor factor along the shock direction are susceptible to growth due their accomodation of plastic deformation. Fabrication of square waves using photolithography and chemical etching was developed to study the nature of plasticity at GBs away from the spall plane. Grains oriented close to <0 1 1> had half the residual amplitudes than grains oriented close to <0 0 1>.
ContributorsBrown, Andrew (Author) / Peralta, Pedro (Committee member) / Mignolet, Marc (Committee member) / Sieradzki, Karl (Committee member) / Solanki, Kiran (Committee member) / Jiang, Hanqing (Committee member) / Arizona State University (Publisher)
Created2015
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Description
An accurate knowledge of the complex microstructure of a heterogeneous material is crucial for quantitative structure-property relations establishment and its performance prediction and optimization. X-ray tomography has provided a non-destructive means for microstructure characterization in both 3D and 4D (i.e., structural evolution over time). Traditional reconstruction algorithms like filtered-back-projection (FBP)

An accurate knowledge of the complex microstructure of a heterogeneous material is crucial for quantitative structure-property relations establishment and its performance prediction and optimization. X-ray tomography has provided a non-destructive means for microstructure characterization in both 3D and 4D (i.e., structural evolution over time). Traditional reconstruction algorithms like filtered-back-projection (FBP) method or algebraic reconstruction techniques (ART) require huge number of tomographic projections and segmentation process before conducting microstructural quantification. This can be quite time consuming and computationally intensive.

In this thesis, a novel procedure is first presented that allows one to directly extract key structural information in forms of spatial correlation functions from limited x-ray tomography data. The key component of the procedure is the computation of a “probability map”, which provides the probability of an arbitrary point in the material system belonging to specific phase. The correlation functions of interest are then readily computed from the probability map. Using effective medium theory, accurate predictions of physical properties (e.g., elastic moduli) can be obtained.

Secondly, a stochastic optimization procedure that enables one to accurately reconstruct material microstructure from a small number of x-ray tomographic projections (e.g., 20 - 40) is presented. Moreover, a stochastic procedure for multi-modal data fusion is proposed, where both X-ray projections and correlation functions computed from limited 2D optical images are fused to accurately reconstruct complex heterogeneous materials in 3D. This multi-modal reconstruction algorithm is proved to be able to integrate the complementary data to perform an excellent optimization procedure, which indicates its high efficiency in using limited structural information.

Finally, the accuracy of the stochastic reconstruction procedure using limited X-ray projection data is ascertained by analyzing the microstructural degeneracy and the roughness of energy landscape associated with different number of projections. Ground-state degeneracy of a microstructure is found to decrease with increasing number of projections, which indicates a higher probability that the reconstructed configurations match the actual microstructure. The roughness of energy landscape can also provide information about the complexity and convergence behavior of the reconstruction for given microstructures and projection number.
ContributorsLi, Hechao (Author) / Jiao, Yang (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Liu, Yongming (Committee member) / Ren, Yi (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2017