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Description
Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a

Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a corrosive environment under a tensile stress. Silver-gold can experience this type of brittle fracture for a range of compositions. The corrosion process in this alloy results in a bicontinuous nanoscale morphology composed of gold-rich ligaments and voids often referred to as nanoporous gold. Experiments have shown that monolithic nanoporous gold can sustain high speed cracks which can then be injected into parent-phase alloy. This work compares nanoporous gold created from ordered and disordered copper-gold using digital image analysis and electron backscatter diffraction. Nanoporous gold from both disordered copper-gold and silver-gold, and ordered copper-gold show that grain orientation and shape remain largely unchanged by the dealloying process. Comparing the morphology of the nanoporous gold from ordered and disordered copper-gold with digital image analysis, minimal differences are found between the two and it is concluded that they are not statistically significant. This reveals the robust nature of nanoporous gold morphology against small variations in surface diffusion and parent-phase crystal structure.
Then the corrosion penetration down the grain boundary is compared to the depth of crack injections in polycrystal silver-gold. Based on statistical comparison, the crack-injections penetrate into the parent-phase grain boundary beyond the corrosion-induced porosity. To compare crack injections to stress-corrosion cracking, single crystal silver-gold samples are employed. Due to the cleavage-like nature of the fracture surfaces, electron backscatter diffraction is possible and employed to compare the crystallography of stress-corrosion crack surfaces and crack-injection surfaces. From the crystallographic similarities of these fracture surfaces, it is concluded that stress-corrosion can occur via a series of crack-injection events. This relationship between crack injections and stress corrosion cracking is further examined using electrochemical data from polycrystal silver-gold samples during stress-corrosion cracking. The results support the idea that crack injection is a mechanism for stress-corrosion cracking.
ContributorsKarasz, Erin (Author) / Sieradzki, Karl (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Peralta, Pedro (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2020
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Description

The rationale of this thesis is to provide a thorough understanding of spalling for semiconductor materials and develop a low temperature spalling technology that reduces the surface roughness of the spalled wafers for Photovoltaics applications.

ContributorsGuimera Coll, Pablo (Author) / Bertoni, Mariana I (Thesis advisor) / Meier, Rico (Committee member) / Holman, Zachary (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2020
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Description
An ongoing effort in the photovoltaic (PV) industry is to reduce the major manufacturing cost components of solar cells, the great majority of which are based on crystalline silicon (c-Si). This includes the substitution of screenprinted silver (Ag) cell contacts with alternative copper (Cu)-based contacts, usually applied with plating. Plated

An ongoing effort in the photovoltaic (PV) industry is to reduce the major manufacturing cost components of solar cells, the great majority of which are based on crystalline silicon (c-Si). This includes the substitution of screenprinted silver (Ag) cell contacts with alternative copper (Cu)-based contacts, usually applied with plating. Plated Cu contact schemes have been under study for many years with only minor traction in industrial production. One of the more commonly-cited barriers to the adoption of Cu-based contacts for photovoltaics is long-term reliability, as Cu is a significant contaminant in c-Si, forming precipitates that degrade performance via degradation of diode character and reduction of minority carrier lifetime. Cu contamination from contacts might cause degradation during field deployment if Cu is able to ingress into c-Si. Furthermore, Cu contamination is also known to cause a form of light-induced degradation (LID) which further degrades carrier lifetime when cells are exposed to light.

Prior literature on Cu-contact reliability tended to focus on accelerated testing at the cell and wafer level that may not be entirely replicative of real-world environmental stresses in PV modules. This thesis is aimed at advancing the understanding of Cu-contact reliability from the perspective of quasi-commercial modules under more realistic stresses. In this thesis, c-Si solar cells with Cu-plated contacts are fabricated, made into PV modules, and subjected to environmental stress in an attempt to induce hypothesized failure modes and understand any new vulnerabilities that Cu contacts might introduce. In particular, damp heat stress is applied to conventional, p-type c-Si modules and high efficiency, n-type c-Si heterojunction modules. I present evidence of Cu-induced diode degradation that also depends on PV module materials, as well as degradation unrelated to Cu, and in either case suggest engineering solutions to the observed degradation. In a forensic search for degradation mechanisms, I present novel evidence of Cu outdiffusion from contact layers and encapsulant-driven contact corrosion as potential key factors. Finally, outdoor exposures to light uncover peculiarities in Cu-plated samples, but do not point to especially serious vulnerabilities.
ContributorsKaras, Joseph (Author) / Bowden, Stuart (Thesis advisor) / Alford, Terry (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Michaelson, Lynne (Committee member) / Arizona State University (Publisher)
Created2020
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Description
There are increasing demands for gas sensors in air quality and human health monitoring applications. The qualifying sensor technology must be highly sensitive towards ppb level gases of interest, such as acetylene (C2H2), hydrogen sulfide (H2S), and volatile organic compounds. Among the commercially available sensor technologies, conductometric gas sensors with

There are increasing demands for gas sensors in air quality and human health monitoring applications. The qualifying sensor technology must be highly sensitive towards ppb level gases of interest, such as acetylene (C2H2), hydrogen sulfide (H2S), and volatile organic compounds. Among the commercially available sensor technologies, conductometric gas sensors with nanoparticles of oxide semiconductors as sensing materials hold significant advantages in cost, size, and cross-compatibility. However, semiconductor gas sensors must overcome some major challenges in thermal stability, sensitivity, humidity interference, and selectivity before potential widespread adoption in air quality and human health monitoring applications.

The focus of this dissertation is to tackle these issues by optimizing the composition and the morphology of the nanoparticles, and by innovating the structure of the sensing film assembled with the nanoparticles. From the nanoparticles perspective, the thermal stability of tin oxide nanoparticles with different Al dopant concentrations was studied, and the results indicate that within certain range of doping concentration, the dopants segregated at the grain surface can improve the thermal stability by stabilizing the grain boundaries.

From the sensing film perspective, a novel self-assembly approach was developed for copper oxide nanosheets and the sensor response towards H2S gas was revealed to decrease monotonically by more than 60% as the number of layers increase from 1 to 300 (thickness: 0.03-10 μm). Moreover, a sensing mechanism study on the humidity influence on H2S detection was performed to gain more understandings of the role of the hydroxyl group in the surface reaction, and humidity independent response was observed in the monolayer film at 325 ℃. With a more precise deposition tool (Langmuir-Blodgett trough), monolayer film of zinc oxide nanowires sensitized with gold catalyst was prepared, and highly sensitive and specific response to C2H2 in the ppb range was observed. Furthermore, the effect of surface topography of the monolayer film on stabilizing noble metal catalyst, and the sensitization mechanism of gold were investigated.

Lastly, a semiconductor sensor array was developed to analyze the composition of gases dissolved in transformer oil to demonstrate the industrial application of this sensor technology.
ContributorsMiao, Jiansong (Author) / Lin, Jerry Y.S. (Thesis advisor) / Forzani, Erica (Committee member) / Liu, Jingyue (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Perovskite solar cells are the next generation organic-inorganic hybrid technology and have achieved remarkable efficiencies comparable to Si-based conventional solar cells. Since their inception in 2009 with an efficiency of 3.9%, they have improved tremendously over the past decade and recently demonstrated 25.2% efficiency for single-junction devices. There are a

Perovskite solar cells are the next generation organic-inorganic hybrid technology and have achieved remarkable efficiencies comparable to Si-based conventional solar cells. Since their inception in 2009 with an efficiency of 3.9%, they have improved tremendously over the past decade and recently demonstrated 25.2% efficiency for single-junction devices. There are a few hurdles, however, that prevent this technology from realizing their full potential, such as stability and toxicity of the perovskites. Apart from solution processing in the fabrication of perovskites, precursor composition plays a major role in determining the quality of the thin film and its general properties. This work studies novel approaches for improving the efficiency and stability of the perovskite solar cells with minimized toxicity. The effect of excess Pb on photo-degradation in MAPbI3 perovskites in an inverted device architecture was studied with a focus on improving stability and efficiency. Precursor concentration with 5% excess Pb was found to be optimal for better efficiency and stability against photo-degradation. Further improvements in efficiency were made possible through the addition of Zirconium Acetylacetonate as a secondary electron buffer layer. A concentration of 1.5mg/ml was found to be optimal for demonstrating better efficiency and stability. Partial substitution of Pb with non-toxic Sr was also studied for improving the stability of inverted devices. Using acetate-derived precursors, 10% Sr was introduced into perovskites for improvements to the stability of the device.

In another study, triple-cation perovskites with FAMACs cations were studied with doping different amounts of Phenyl Ethyl Ammonium (PEA) to induce a quasi 2D-3D structure for improved moisture stability. Doping the perovskite with 1.67% PEA was found to be best for improved morphology with fewer pinholes, which further resulted in better VOC and stability. A passivation effect for triple-cation perovskites was further proposed with the addition of a Guanidinium Iodide layer on the perovskite. Concentrations of 1mg/ml and 2mg/ml were demonstrated to be best for reducing defects and trap states and increasing the overall stability of the device.
ContributorsYerramilli, Aditya (Author) / Alford, Terry (Thesis advisor) / Theodore, David (Committee member) / Chen, Yuanqing (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Single-layer pentagonal materials have received limited attention compared with their counterparts with hexagonal structures. They are two-dimensional (2D) materials with pentagonal structures, that exhibit novel electronic, optical, or magnetic properties. There are 15 types of pentagonal tessellations which allow plenty of options for constructing 2D pentagonal lattices. Few of them

Single-layer pentagonal materials have received limited attention compared with their counterparts with hexagonal structures. They are two-dimensional (2D) materials with pentagonal structures, that exhibit novel electronic, optical, or magnetic properties. There are 15 types of pentagonal tessellations which allow plenty of options for constructing 2D pentagonal lattices. Few of them have been explored theoretically or experimentally. Studying this new type of 2D materials with density functional theory (DFT) will inspire the discovery of new 2D materials and open up applications of these materials in electronic and magnetic devices.In this dissertation, DFT is applied to discover novel 2D materials with pentagonal structures. Firstly, I examine the possibility of forming a 2D nanosheet with the vertices of type 15 pentagons occupied by boron, silicon, phosphorous, sulfur, gallium, germanium or tin atoms. I obtain different rearranged structures such as a single-layer gallium sheet with triangular patterns. Then the exploration expands to other 14 types of pentagons, leading to the discoveries of carbon nanosheets with Cairo tessellation (type 2/4 pentagons) and other patterns. The resulting 2D structures exhibit diverse electrical properties. Then I reveal the hidden Cairo tessellations in the pyrite structures and discover a family of planar 2D materials (such as PtP2), with a chemical formula of AB2 and space group pa ̄3. The combination of DFT and geometries opens up a novel route for the discovery of new 2D materials. Following this path, a series of 2D pentagonal materials such as 2D CoS2 are revealed with promising electronic and magnetic applications. Specifically, the DFT calculations show that CoS2 is an antiferromagnetic semiconductor with a band gap of 2.24 eV, and a N ́eel temperature of about 20 K. In order to enhance the superexchange interactions between the ions in this binary compound, I explore the ternary 2D pentagonal material CoAsS, that lacks the inversion symmetry. I find out CoAsS exhibits a higher Curie temperature of 95 K and a sizable piezoelectricity (d11=-3.52 pm/V). In addition to CoAsS, 34 ternary 2D pentagonal materials are discovered, among which I focus on FeAsS, that is a semiconductor showing strong magnetocrystalline anisotropy and sizable Berry curvature. Its magnetocrystalline anisotropy energy is 440 μeV/Fe ion, higher than many other 2D magnets that have been found.
Overall, this work not only provides insights into the structure-property relationship of 2D pentagonal materials and opens up a new route of studying 2D materials by combining geometry and computational materials science, but also shows the potential applications of 2D pentagonal materials in electronic and magnetic devices.
ContributorsLiu, Lei (Author) / Zhuang, Houlong (Thesis advisor) / Singh, Arunima (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Energy return in footwear is associated with the damping behavior of midsole foams, which stems from the combination of cellular structure and polymeric material behavior. Recently, traditional ethyl vinyl acetate (EVA) foams have been replaced by BOOST(TM) foams, thereby reducing the energetic cost of running. These are bead foams made

Energy return in footwear is associated with the damping behavior of midsole foams, which stems from the combination of cellular structure and polymeric material behavior. Recently, traditional ethyl vinyl acetate (EVA) foams have been replaced by BOOST(TM) foams, thereby reducing the energetic cost of running. These are bead foams made from expanded thermoplastic polyurethane (eTPU), which have a multi-scale structure consisting of fused porous beads, at the meso-scale, and thousands of small closed cells within the beads at the micro-scale. Existing predictive models coarsely describe the macroscopic behavior but do not take into account strain localizations and microstructural heterogeneities. Thus, enhancement in material performance and optimization requires a comprehensive understanding of the foam’s cellular structure at all length scales and its influence on mechanical response.

This dissertation focused on characterization and deformation behavior of eTPU bead foams with a unique graded cell structure at the micro and meso-scale. The evolution of the foam structure during compression was studied using a combination of in situ lab scale and synchrotron x-ray tomography using a four-dimensional (4D, deformation + time) approach. A digital volume correlation (DVC) method was developed to elucidate the role of cell structure on local deformation mechanisms. The overall mechanical response was also studied ex situ to probe the effect of cell size distribution on the force-deflection behavior. The radial variation in porosity and ligament thickness profoundly influenced the global mechanical behavior. The correlation of changes in void size and shape helped in identifying potentially weak regions in the microstructure. Strain maps showed the initiation of failure in cell structure and it was found to be influenced by the heterogeneities around the immediate neighbors in a cluster of voids. Poisson’s ratio evaluated from DVC was related to the microstructure of the bead foams. The 4D approach taken here provided an in depth and mechanistic understanding of the material behavior, both at the bead and plate levels, that will be invaluable in designing the next generation of high-performance footwear.
ContributorsSundaram Singaravelu, Arun Sundar (Author) / Chawla, Nikhilesh (Thesis advisor) / Emady, Heather (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Deformable heat exchangers could provide a multitude of previously untapped advantages ranging from adaptable performance via macroscale, dynamic shape change (akin to dilation/constriction seen in blood vessels) to enhanced heat transfer at thermal interfaces through microscale, surface deformations. So far, making deformable, ‘soft heat exchangers’ (SHXs) has been limited by

Deformable heat exchangers could provide a multitude of previously untapped advantages ranging from adaptable performance via macroscale, dynamic shape change (akin to dilation/constriction seen in blood vessels) to enhanced heat transfer at thermal interfaces through microscale, surface deformations. So far, making deformable, ‘soft heat exchangers’ (SHXs) has been limited by the low thermal conductivity of materials with suitable mechanical properties. The recent introduction of liquid-metal embedded elastomers by Bartlett et al1 has addressed this need. Specifically, by remaining soft and stretchable despite the addition of filler, these thermally conductive composites provide an ideal material for the new class of “soft thermal systems”, which is introduced in this work. Understanding such thermal systems will be a key element in enabling technology that require high levels of stretchability, such as thermoregulatory garments, soft electronics, wearable electronics, and high-powered robotics. Shape change inherent to SHX operation has the potential to violate many conventional assumptions used in HX design and thus requires the development of new theoretical approaches to predict performance. To create a basis for understanding these devices, this work highlights two sequential studies. First, the effects of transitioning to a surface deformable, SHX under steady state static conditions in the setting of a liquid cooling device for thermoregulation, electronics and robotics applications was explored. In this study, a thermomechanical model was built and validated to predict the thermal performance and a system wide analysis to optimize such devices was carried out. Second, from a more fundamental perspective, the effects of SHXs undergoing transient shape deformation during operation was explored. A phase shift phenomenon in cooling performance dependent on stretch rate, stretch extent and thermal diffusivity was discovered and explained. With the use of a time scale analysis, the extent of quasi-static assumption viability in modeling such systems was quantified and multiple shape modulation regime limits were defined. Finally, nuance considerations and future work of using liquid metal-silicone composites in SHXs were discussed.
ContributorsKotagama, Praveen (Author) / Rykaczewski, Konrad (Thesis advisor) / Wang, Robert (Committee member) / Phelan, Patrick (Committee member) / Herrmann, Marcus (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2020
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Description
The maximum theoretical efficiency of a terrestrial non-concentrated silicon solar cell is 29.4%, as obtained from detailed balance analysis. Over 90% of the current silicon photovoltaics market is based on solar cells with diffused junctions (Al-BSF, PERC, PERL, etc.), which are limited in performance by increased non-radiative recombination in the

The maximum theoretical efficiency of a terrestrial non-concentrated silicon solar cell is 29.4%, as obtained from detailed balance analysis. Over 90% of the current silicon photovoltaics market is based on solar cells with diffused junctions (Al-BSF, PERC, PERL, etc.), which are limited in performance by increased non-radiative recombination in the doped regions. This limitation can be overcome through the use of passivating contacts, which prevent recombination at the absorber interfaces while providing the selectivity to efficiently separate the charge carriers generated in the absorber. This thesis aims at developing an understanding of how the material properties of the contact affect device performance through simulations.The partial specific contact resistance framework developed by Onno et al. aims to link material behavior to device performance specifically at open circuit. In this thesis, the framework is expanded to other operating points of a device, leading to a model for calculating the partial contact resistances at any current flow. The error in calculating these resistances is irrelevant to device performance resulting in an error in calculating fill factor from resistances below 0.1% when the fill factors of the cell are above 70%, i.e., for cells with good passivation and selectivity.
Further, silicon heterojunction (SHJ) and tunnel-oxide based solar cells are simulated in 1D finite-difference modeling package AFORS-HET. The effects of material property changes on device performance are investigated using novel contact materials like Al0.8Ga0.2As (hole contact for SHJ) and ITO (electron contact for tunnel-oxide cells). While changing the bandgap and electron affinity of the contact affect the height of the Schottky barrier and hence contact resistivity, increasing the doping of the contact will increase its selectivity. In the case of ITO, the contact needs to have a work function below 4.2 eV to be electron selective, which suggests that other low work function TCOs (like AZO) will be more applicable as alternative dopant-free electron contacts. The AFORS-HET model also shows that buried doped regions arising from boron diffusion in the absorber can damage passivation and decrease the open circuit voltage of the device.
ContributorsDasgupta, Sagnik (Author) / Holman, Zachary (Thesis advisor) / Onno, Arthur (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Lateral programmable metallization cells (PMC) utilize the properties of electrodeposits grown over a solid electrolyte channel. Such devices have an active anode and an inert cathode separated by a long electrodeposit channel in a coplanar arrangement. The ability to transport large amount of metallic mass across the channel makes these

Lateral programmable metallization cells (PMC) utilize the properties of electrodeposits grown over a solid electrolyte channel. Such devices have an active anode and an inert cathode separated by a long electrodeposit channel in a coplanar arrangement. The ability to transport large amount of metallic mass across the channel makes these devices attractive for various More-Than-Moore applications. Existing literature lacks a comprehensive study of electrodeposit growth kinetics in lateral PMCs. Moreover, the morphology of electrodeposit growth in larger, planar devices is also not understood. Despite the variety of applications, lateral PMCs are not embraced by the semiconductor industry due to incompatible materials and high operating voltages needed for such devices. In this work, a numerical model based on the basic processes in PMCs – cation drift and redox reactions – is proposed, and the effect of various materials parameters on the electrodeposit growth kinetics is reported. The morphology of the electrodeposit growth and kinetics of the electrodeposition process are also studied in devices based on Ag-Ge30Se70 materials system. It was observed that the electrodeposition process mainly consists of two regimes of growth – cation drift limited regime and mixed regime. The electrodeposition starts in cation drift limited regime at low electric fields and transitions into mixed regime as the field increases. The onset of mixed regime can be controlled by applied voltage which also affects the morphology of electrodeposit growth. The numerical model was then used to successfully predict the device kinetics and onset of mixed regime. The problem of materials incompatibility with semiconductor manufacturing was solved by proposing a novel device structure. A bilayer structure using semiconductor foundry friendly materials was suggested as a candidate for solid electrolyte. The bilayer structure consists of a low resistivity oxide shunt layer on top of a high resistivity ion carrying oxide layer. Devices using Cu2O as the low resistivity shunt on top of Cu doped WO3 oxide were fabricated. The bilayer devices provided orders of magnitude improvement in device performance in the context of operating voltage and switching time. Electrical and materials characterization revealed the structure of bilayers and the mechanism of electrodeposition in these devices.
ContributorsChamele, Ninad (Author) / Kozicki, Michael (Thesis advisor) / Barnaby, Hugh (Committee member) / Newman, Nathan (Committee member) / Gonzalez-Velo, Yago (Committee member) / Arizona State University (Publisher)
Created2020