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- All Subjects: Materials Science
- Creators: Krause, Stephen
Description
Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to be operated at a high temperature (∼1000 °C), are expensive, and have slow response to changes in energy demands. One important need for commercialization of SOFCs is a lowering of their operating temperature, which requires an electrolyte that can operate at lower temperatures. Doped ceria is one such candidate. For this dissertation work I have studied different types of doped ceria to understand the mechanism of oxygen vacancy diffusion through the bulk. Doped ceria is important because they have high ionic conductivities thus making them attractive candidates for the electrolytes of solid oxide fuel cells. In particular, I have studied how the ionic conductivities are improved in these doped materials by studying the oxygen-vacancy formations and migrations. In this dissertation I describe the application of density functional theory (DFT) and Kinetic Lattice Monte Carlo (KLMC) simulations to calculate the vacancy diffusion and ionic conductivities in doped ceria. The dopants used are praseodymium (Pr), gadolinium (Gd), and neodymium (Nd), all belonging to the lanthanide series. The activation energies for vacancy migration between different nearest neighbor (relative to the dopant) positions were calculated using the commercial DFT code VASP (Vienna Ab-initio Simulation Package). These activation energies were then used as inputs to the KLMC code that I co-developed. The KLMC code was run for different temperatures (673 K to 1073 K) and for different dopant concentrations (0 to 40%). These simulations have resulted in the prediction of dopant concentrations for maximum ionic conductivity at a given temperature.
ContributorsAnwar, Shahriar (Author) / Adams, James B (Thesis advisor) / Crozier, Peter (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
Amorphous oxide semiconductors are promising new materials for various optoelectronic applications. In this study, improved electrical and optical properties upon thermal and microwave processing of mixed-oxide semiconductors are reported. First, arsenic-doped silicon was used as a model system to understand susceptor-assisted microwave annealing. Mixed oxide semiconductor films of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) were deposited by room-temperature RF sputtering on flexible polymer substrates. Thermal annealing in different environments - air, vacuum and oxygen was done. Electrical and optical characterization was carried out before and after annealing. The degree of reversal in the degradation in electrical properties of the thin films upon annealing in oxygen was assessed by subjecting samples to subsequent vacuum anneals. To further increase the conductivity of the IGZO films, Ag layers of various thicknesses were embedded between two IGZO layers. Optical performance of the multilayer structures was improved by susceptor-assisted microwave annealing and furnace-annealing in oxygen environment without compromising on their electrical conductivity. The post-processing of the films in different environments was used to develop an understanding of mechanisms of carrier generation, transport and optical absorption. This study establishes IGZO as a viable transparent conductor, which can be deposited at room-temperature and processed by thermal and microwave annealing to improve electrical and optical performance for applications in flexible electronics and optoelectronics.
ContributorsGadre, Mandar (Author) / Alford, Terry L. (Thesis advisor) / Schroder, Dieter (Committee member) / Krause, Stephen (Committee member) / Theodore, David (Committee member) / Arizona State University (Publisher)
Created2011
Description
Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data.
ContributorsMathews, Jay (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Drucker, Jeffery (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2011
Description
Increasing demand for high strength powder metallurgy (PM) steels has resulted in the development of dual phase PM steels. In this work, the effects of thermal aging on the microstructure and mechanical behavior of dual phase precipitation hardened powder metallurgy (PM) stainless steels of varying ferrite-martensite content were examined. Quantitative analyses of the inherent porosity and phase fractions were conducted on the steels and no significant differences were noted with respect to aging temperature. Tensile strength, yield strength, and elongation to fracture all increased with increasing aging temperature reaching maxima at 538oC in most cases. Increased strength and decreased ductility were observed in steels of higher martensite content. Nanoindentation of the individual microconstituents was employed to obtain a fundamental understanding of the strengthening contributions. Both the ferrite and martensite hardness values increased with aging temperature and exhibited similar maxima to the bulk tensile properties. Due to the complex non-uniform stresses and strains associated with conventional nanoindentation, micropillar compression has become an attractive method to probe local mechanical behavior while limiting strain gradients and contributions from surrounding features. In this study, micropillars of ferrite and martensite were fabricated by focused ion beam (FIB) milling of dual phase precipitation hardened powder metallurgy (PM) stainless steels. Compression testing was conducted using a nanoindenter equipped with a flat punch indenter. The stress-strain curves of the individual microconstituents were calculated from the load-displacement curves less the extraneous displacements of the system. Using a rule of mixtures approach in conjunction with porosity corrections, the mechanical properties of ferrite and martensite were combined for comparison to tensile tests of the bulk material, and reasonable agreement was found for the ultimate tensile strength. Micropillar compression experiments of both as sintered and thermally aged material allowed for investigation of the effect of thermal aging.
ContributorsStewart, Jennifer (Author) / Chawla, Nikhilesh (Thesis advisor) / Jiang, Hanqing (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
In recent years, the field of nanomedicine has progressed at an astonishing rate, particularly with respect to applications in cancer treatment and molecular imaging. Although organic systems have been the frontrunners, inorganic systems have also begun to show promise, especially those based upon silica and magnetic nanoparticles (NPs). Many of these systems are being designed for simultaneous therapeutic and diagnostic capabilities, thus coining the term, theranostics. A unique class of inorganic systems that shows great promise as theranostics is that of layered double hydroxides (LDH). By synthesis of a core/shell structures, e.g. a gold nanoparticle (NP) core and LDH shell, the multifunctional theranostic may be developed without a drastic increase in the structural complexity. To demonstrate initial proof-of-concept of a potential (inorganic) theranostic platform, a Au-core/LDH-shell nanovector has been synthesized and characterized. The LDH shell was heterogeneously nucleated and grown on the surface of silica coated gold NPs via a coprecipitation method. Polyethylene glycol (PEG) was introduced in the initial synthesis steps to improve crystallinity and colloidal stability. Additionally, during synthesis, fluorescein isothiocyanate (FITC) was intercalated into the interlayer spacing of the LDH. In contrast to the PEG stabilization, a post synthesis citric acid treatment was used as a method to control the size and short-term stability. The heterogeneous core-shell system was characterized with scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), dynamic light scattering (DLS), and powder x-ray diffraction (PXRD). A preliminary in vitro study carried out with the assistance of Dr. Kaushal Rege's group at Arizona State University was to demonstrate the endocytosis capability of homogeneously-grown LDH NPs. The DLS measurements of the core-shell NPs indicated an average particle size of 212nm. The PXRD analysis showed that PEG greatly improved the crystallinity of the system while simultaneously preventing aggregation of the NPs. The preliminary in vitro fluorescence microscopy revealed a moderate uptake of homogeneous LDH NPs into the cells.
ContributorsRearick, Colton (Author) / Dey, Sandwip K (Thesis advisor) / Krause, Stephen (Committee member) / Ramakrishna, B (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis discusses the use of low temperature microwave anneal as an alternative technique to recrystallize materials damaged or amorphized due to implantation techniques. The work focuses on the annealing of high-Z doped Si wafers that are incapable of attaining high temperatures required for recrystallizing the damaged implanted layers by microwave absorption The increasing necessity for quicker and more efficient processing techniques motivates study of the use of a single frequency applicator microwave cavity along with a Fe2O3 infused SiC-alumina susceptor/applicator as an alternative post implantation process. Arsenic implanted Si samples of different dopant concentrations and implantation energies were studied pre and post microwave annealing. A set of as-implanted Si samples were also used to assess the effect of inactive dopants against presence of electrically active dopants on the recrystallization mechanisms. The extent of damage repair and Si recrystallization of the damage caused by arsenic and Si implantation of Si is determined by cross-section transmission electron microscopy and Raman spectroscopy. Dopant activation is evaluated for the As implanted Si by sheet resistance measurements. For the same, secondary ion mass spectroscopy analysis is used to compare the extent of diffusion that results from such microwave annealing with that experienced when using conventional rapid thermal annealing (RTA). Results show that compared to susceptor assisted microwave annealing, RTA caused undesired dopant diffusion. The SiC-alumina susceptor plays a predominant role in supplying heat to the Si substrate, and acts as an assistor that helps a high-Z dopant like arsenic to absorb the microwave energy using a microwave loss mechanism which is a combination of ionic and dipole losses. Comparisons of annealing of the samples were done with and without the use of the susceptor, and confirm the role played by the susceptor, since the samples donot recrystallize when the surface heating mechanism provided by the susceptor is not incorporated. Variable frequency microwave annealing was also performed over the as-implanted Si samples for durations and temperatures higher than the single frequency microwave anneal, but only partial recrystallization of the damaged layer was achieved.
ContributorsVemuri, Rajitha (Author) / Alford, Terry L. (Thesis advisor) / Theodore, David (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
Thin films of ever reducing thickness are used in a plethora of applications and their performance is highly dependent on their microstructure. Computer simulations could then play a vital role in predicting the microstructure of thin films as a function of processing conditions. FACET is one such software tool designed by our research group to model polycrystalline thin film growth, including texture evolution and grain growth of polycrystalline films in 2D. Several modifications to the original FACET code were done to enhance its usability and accuracy. Simulations of sputtered silver thin films are presented here with FACET 2.0 with qualitative and semi-quantitative comparisons with previously published experimental results. Comparisons of grain size, texture and film thickness between simulations and experiments are presented which describe growth modes due to various deposition factors like flux angle and substrate temperature. These simulations provide reasonable agreement with the experimental data over a diverse range of process parameters. Preliminary experiments in depositions of Silver films are also attempted with varying substrates and thickness in order to generate complementary experimental and simulation studies of microstructure evolution. Overall, based on the comparisons, FACET provides interesting insights into thin film growth processes, and the effects of various deposition conditions on thin film structure and microstructure. Lastly, simple molecular dynamics simulations of deposition on bi-crystals are attempted for gaining insight into texture based grain competition during film growth. These simulations predict texture based grain coarsening mechanisms like twinning and grain boundary migration that have been commonly reported in FCC films.
ContributorsRairkar, Asit (Author) / Adams, James B (Thesis advisor) / Krause, Stephen (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2011
Description
Raman scattering from Ge-Si core-shell nanowires is investigated theoretically and experimentally. A theoretical model that makes it possible to extract quantitative strain information from the measured Raman spectra is presented for the first time. Geometrical and elastic simplifications are introduced to keep the model analytical, which facilitates comparison with experimental results. In particular, the nanowires are assumed to be cylindrical, and their elastic constants isotropic. The simple analytical model is subsequently validated by performing numerical calculations using realistic nanowire geometries and cubic, anisotropic elastic constants. The comparison confirms that the analytic model is an excellent approximation that greatly facilitates quantitative Raman work, with expected errors in the strain determination that do not exceed 10%. Experimental Raman spectra of a variety of core-shell nanowires are presented, and the strain in the nanowires is assessed using the models described above. It is found that all structures present a significant degree of strain relaxation relative to ideal, fully strained Ge-Si core-shell structures. The analytical models are modified to quantify this strain relaxation.
ContributorsSingh, Rachna (Author) / Menéndez, Jose (Thesis advisor) / Drucker, Jeffery (Committee member) / Ponce, Fernando (Committee member) / Tsen, Kong-Thon (Committee member) / Bennett, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
Electromigration in metal interconnects is the most pernicious failure mechanism in semiconductor integrated circuits (ICs). Early electromigration investigations were primarily focused on aluminum interconnects for silicon-based ICs. An alternative metallization compatible with gallium arsenide (GaAs) was required in the development of high-powered radio frequency (RF) compound semiconductor devices operating at higher current densities and elevated temperatures. Gold-based metallization was implemented on GaAs devices because it uniquely forms a very low resistance ohmic contact and gold interconnects have superior electrical and thermal conductivity properties. Gold (Au) was also believed to have improved resistance to electromigration due to its higher melting temperature, yet electromigration reliability data on passivated Au interconnects is scarce and inadequate in the literature. Therefore, the objective of this research was to characterize the electromigration lifetimes of passivated Au interconnects under precisely controlled stress conditions with statistically relevant quantities to obtain accurate model parameters essential for extrapolation to normal operational conditions. This research objective was accomplished through measurement of electromigration lifetimes of large quantities of passivated electroplated Au interconnects utilizing high-resolution in-situ resistance monitoring equipment. Application of moderate accelerated stress conditions with a current density limited to 2 MA/cm2 and oven temperatures in the range of 300°C to 375°C avoided electrical overstress and severe Joule-heated temperature gradients. Temperature coefficients of resistance (TCRs) were measured to determine accurate Joule-heated Au interconnect film temperatures. A failure criterion of 50% resistance degradation was selected to prevent thermal runaway and catastrophic metal ruptures that are problematic of open circuit failure tests. Test structure design was optimized to reduce resistance variation and facilitate failure analysis. Characterization of the Au microstructure yielded a median grain size of 0.91 ìm. All Au lifetime distributions followed log-normal distributions and Black's model was found to be applicable. An activation energy of 0.80 ± 0.05 eV was measured from constant current electromigration tests at multiple temperatures. A current density exponent of 1.91 was extracted from multiple current densities at a constant temperature. Electromigration-induced void morphology along with these model parameters indicated grain boundary diffusion is dominant and the void nucleation mechanism controlled the failure time.
ContributorsKilgore, Stephen (Author) / Adams, James (Thesis advisor) / Schroder, Dieter (Thesis advisor) / Krause, Stephen (Committee member) / Gaw, Craig (Committee member) / Arizona State University (Publisher)
Created2013
Description
This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches.
ContributorsXu, Chi (Author) / Kouvetakis, John (Thesis advisor) / Menéndez, Jose (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Drucker, Jeffrey (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2013