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Description
Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are essential for interpreting Martian mineralogy and geologic history. However, previous studies have shown that chemical weathering and the precipitation of fine-grained secondary silicates can adversely affect the accuracy of TIR spectral models. Furthermore, spectral libraries used to identify minerals on the Martian surface lack some important weathering products, including poorly-crystalline aluminosilicates like allophane, thus eliminating their identification in TIR spectral models. It is essential to accurately interpret TIR spectral data from chemically weathered surfaces to understand the evolution of aqueous processes on Mars. Laboratory experiments were performed to improve interpretations of TIR data from weathered surfaces. To test the accuracy of deriving chemistry of weathered rocks from TIR spectroscopy, chemistry was derived from TIR models of weathered basalts from Baynton, Australia and compared to actual weathering rind chemistry. To determine how specific secondary silicates affect the TIR spectroscopy of weathered basalts, mixtures of basaltic minerals and small amounts of secondary silicates were modeled. Poorly-crystalline aluminosilicates were synthesized and their TIR spectra were added to spectral libraries. Regional Thermal Emission Spectrometer (TES) data were modeled using libraries containing these poorly-crystalline aluminosilicates to test for their presence on the Mars. Chemistry derived from models of weathered Baynton basalts is not accurate, but broad chemical weathering trends can be interpreted from the data. TIR models of mineral mixtures show that small amounts of crystalline and amorphous silicate weathering products (2.5-5 wt.%) can be detected in TIR models and can adversely affect modeled plagioclase abundances. Poorly-crystalline aluminosilicates are identified in Northern Acidalia, Solis Planum, and Meridiani. Previous studies have suggested that acid sulfate weathering was the dominant surface alteration process for the past 3.5 billion years; however, the identification of allophane indicates that alteration at near-neutral pH occurred on regional scales and that acid sulfate weathering is not the only weathering process on Mars.
ContributorsRampe, Elizabeth Barger (Author) / Sharp, Thomas G (Thesis advisor) / Christensen, Phillip (Committee member) / Hervig, Richard (Committee member) / Shock, Everett (Committee member) / Williams, Lynda (Committee member) / Arizona State University (Publisher)
Created2011
Description
Applications of non-traditional stable isotope variations are moving beyond geosciences to biomedicine, made possible by advances in multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) technology. Mass-dependent isotope variation can provide information about the sources of elements and the chemical reactions that they undergo. Iron and calcium isotope systematics in biomedicine are relatively unexplored but have great potential scientific interest due to their essential nature in metabolism. Iron, a crucial element in biology, fractionates during biochemically relevant reactions. To test the extent of this fractionation in an important reaction process, equilibrium iron isotope fractionation during organic ligand exchange was determined. The results show that iron fractionates during organic ligand exchange, and that isotope enrichment increases as a function of the difference in binding constants between ligands. Additionally, to create a mass balance model for iron in a whole organism, iron isotope compositions in a whole mouse and in individual mouse organs were measured. The results indicate that fractionation occurs during transfer between individual organs, and that the whole organism was isotopically light compared with food. These two experiments advance our ability to interpret stable iron isotopes in biomedicine. Previous research demonstrated that calcium isotope variations in urine can be used as an indicator of changes in net bone mineral balance. In order to measure calcium isotopes by MC-ICP-MS, a chemical purification method was developed to quantitatively separate calcium from other elements in a biological matrix. Subsequently, this method was used to evaluate if calcium isotopes respond when organisms are subjected to conditions known to induce bone loss: 1) Rhesus monkeys were given an estrogen-suppressing drug; 2) Human patients underwent extended bed rest. In both studies, there were rapid, detectable changes in calcium isotope compositions from baseline - verifying that calcium isotopes can be used to rapidly detect changes in bone mineral balance. By characterizing iron isotope fractionation in biologically relevant processes and by demonstrating that calcium isotopes vary rapidly in response to bone loss, this thesis represents an important step in utilizing these isotope systems as a diagnostic and mechanistic tool to study the metabolism of these elements in vivo.
ContributorsMorgan, Jennifer Lynn Louden (Author) / Anbar, Ariel D. (Thesis advisor) / Wasylenki, Laura E. (Committee member) / Jones, Anne K. (Committee member) / Shock, Everett (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
In this study, the influence of fluid mixing on temperature and geochemistry of hot spring fluids is investigated. Yellowstone National Park (YNP) is home to a diverse range of hot springs with varying temperature and chemistry. The mixing zone of interest in this paper, located in Geyser Creek, YNP, has been a point of interest since at least the 1960’s (Raymahashay, 1968). Two springs, one basic (~pH 7) and one acidic (~pH 3) mix together down an outflow channel. There are visual bands of different photosynthetic pigments which suggests the creation of temperature and chemical gradients due to the fluids mixing. In this study, to determine if fluid mixing is driving these changes of temperature and chemistry in the system, a model that factors in evaporation and cooling was developed and compared to measured temperature and chemical data collected downstream. Comparison of the modeled temperature and chemistry to the measured values at the downstream mixture shows that many of the ions, such as Cl⁻, F⁻, and Li⁺, behave conservatively with respect to mixing. This indicates that the influence of mixing accounts for a large proportion of variation in the chemical composition of the system. However, there are some chemical constituents like CH₄, H₂, and NO₃⁻, that were not conserved, and the concentrations were either depleted or increased in the downstream mixture. Some of these constituents are known to be used by microorganisms. The development of this mixing model can be used as a tool for predicting biological activity as well as building the framework for future geochemical and computational models that can be used to understand the energy availability and the microbial communities that are present.
ContributorsOrrill, Brianna Isabel (Author) / Shock, Everett (Thesis director) / Howells, Alta (Committee member) / School of Life Sciences (Contributor) / School of Earth and Space Exploration (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
A new challenge on the horizon is to utilize the large amounts of protein found in the atmosphere to identify different organisms from which the protein originated. Included here is work investigating the presence of identifiable patterns of different proteins collected from the air and biological samples for the purposes of remote identification. Protein patterns were generated using high performance liquid chromatography (HPLC). Patterns created could identify high-traffic and low-traffic indoor spaces. Samples were collected from the air using air pumps to draw air through a filter paper trapping particulates, including large amounts of shed protein matter. In complimentary research aerosolized biological samples were collected from various ecosystems throughout Ecuador to explore the relationship between environmental setting and aerosolized protein concentrations. In order to further enhance protein separation and produce more detailed patterns for the identification of individual organisms of interest; a novel separation device was constructed and characterized. The separation device incorporates a longitudinal gradient as well as insulating dielectrophoretic features within a single channel. This design allows for the production of stronger local field gradients along a global gradient allowing particles to enter, initially transported through the channel by electrophoresis and electroosmosis, and to be isolated according to their characteristic physical properties, including charge, polarizability, deformability, surface charge mobility, dielectric features, and local capacitance. Thus, different types of particles are simultaneously separated at different points along the channel distance given small variations of properties. The device has shown the ability to separate analytes over a large dynamic range of size, from 20 nm to 1 μm, roughly the size of proteins to the size of cells. In the study of different sized sulfate capped polystyrene particles were shown to be selectively captured as well as concentrating particles from 103 to 106 times. Qualitative capture and manipulation of β-amyloid fibrils were also shown. The results demonstrate the selective focusing ability of the technique; and it may form the foundation for a versatile tool for separating complex mixtures. Combined this work shows promise for future identification of individual organisms from aerosolized protein as well as for applications in biomedical research.
ContributorsStaton, Sarah J. R (Author) / Hayes, Mark A. (Committee member) / Anbar, Ariel D (Committee member) / Shock, Everett (Committee member) / Williams, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
As existing solar cell technologies come closer to their theoretical efficiency, new concepts that overcome the Shockley-Queisser limit and exceed 50% efficiency need to be explored. New materials systems are often investigated to achieve this, but the use of existing solar cell materials in advanced concept approaches is compelling for multiple theoretical and practical reasons. In order to include advanced concept approaches into existing materials, nanostructures are used as they alter the physical properties of these materials. To explore advanced nanostructured concepts with existing materials such as III-V alloys, silicon and/or silicon/germanium and associated alloys, fundamental aspects of using these materials in advanced concept nanostructured solar cells must be understood. Chief among these is the determination and predication of optimum electronic band structures, including effects such as strain on the band structure, and the material's opto-electronic properties. Nanostructures have a large impact on band structure and electronic properties through quantum confinement. An additional large effect is the change in band structure due to elastic strain caused by lattice mismatch between the barrier and nanostructured (usually self-assembled QDs) materials. To develop a material model for advanced concept solar cells, the band structure is calculated for single as well as vertical array of quantum dots with the realistic effects such as strain, associated with the epitaxial growth of these materials. The results show significant effect of strain in band structure. More importantly, the band diagram of a vertical array of QDs with different spacer layer thickness show significant change in band offsets, especially for heavy and light hole valence bands when the spacer layer thickness is reduced. These results, ultimately, have significance to develop a material model for advance concept solar cells that use the QD nanostructures as absorbing medium. The band structure calculations serve as the basis for multiple other calculations. Chief among these is that the model allows the design of a practical QD advanced concept solar cell, which meets key design criteria such as a negligible valence band offset between the QD/barrier materials and close to optimum band gaps, resulting in the predication of optimum material combinations.
ContributorsDahal, Som Nath (Author) / Honsberg, Christiana (Thesis advisor) / Goodnick, Stephen (Committee member) / Roedel, Ronald (Committee member) / Ponce, Fernando (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
ABSTRACT Group III-nitride semiconductor materials have been commercially used in fabrication of light-emitting diodes (LEDs) and laser diodes (LDs) covering the spectral range from UV to visible and infrared, and exhibit unique properties suitable for modern optoelectronic applications. Great advances have recently happened in the research and development in high-power and high-efficiency blue-green-white LEDs, blue LDs and other optoelectronic applications. However, there are still many unsolved challenges with these materials. In this dissertation, several issues concerning structural, electronic and optical properties of III-nitrides have been investigated using a combination of transmission electron microscopy (TEM), electron holography (EH) and cathodoluminescence (CL) techniques. First, a trend of indium chemical inhomogeneity has been found as the indium composition increases for the InGaN epitaxial layers grown by hydride vapor phase epitaxy. Second, different mechanisms contributing to the strain relaxation have been studied for non-polar InGaN epitaxial layers grown on zinc oxide (ZnO) substrate. Third, various structural morphologies of non-polar InGaN epitaxial layers grown on free-standing GaN substrate have been investigated. Fourth, the effect of the growth temperature on the performance of GaN lattice-matched InAlN electron blocking layers has been studied. Finally, the electronic and optical properties of GaN nanowires containing a AlN/GaN superlattice structure have been investigated showing relatively small internal electric field and superlattice- and defect-related emissions along the nanowires.
ContributorsSun, Kewei (Author) / Ponce, Fernando (Thesis advisor) / Smith, David (Committee member) / Treacy, Michael (Committee member) / Drucker, Jeffery (Committee member) / Schmidt, Kevin (Committee member) / Arizona State University (Publisher)
Created2011
Raman spectroscopy characterization of anharmonicity and alloying effects in semiconductor materials
Description
The chemical sensitivity and spatial resolution of Raman spectroscopy, combined with the sensitivity of modern systems that can easily detect single atomic layers, have made this technique a preferred choice for the strain characterization of complex systems such as nanoscale complementary metal-oxide-semiconductor - CMOS - devices. A disadvantage of Raman spectroscopy, however, is that the shifts associated with strain are not related to the geometrical deformations in any obvious way, so that careful calibrations are needed to determine the anharmonic coefficients (p, q and r) that relate strain to Raman shifts. A new set of measurements of the Raman shift in strained Ge films grown on relaxed SiGe buffer layers deposited on Si substrates is presented, and thereby, a new consistent set of values for the parameters p and q for Ge has been proposed. In this dissertation the study of the vibrational properties of Ge1-xSnx alloys has also been reported. The temperature dependence of the Raman spectrum of Ge-rich Ge1-x Snx and Ge1-x-ySi xSny alloys has been determined in the 10 K - 450 K range. The Raman line shift and width changes as a function of temperature are found to be virtually identical to those observed in bulk Ge. This result shows that the anharmonic decay process responsible for the temperature dependence is extremely robust against the alloy perturbation.
ContributorsBagchi, Sampriti (Author) / Menéndez, Jose (Thesis advisor) / Treacy, Michael (Committee member) / Ponce, Fernando (Committee member) / Tsen, Kong-Thon (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
Meteorology is an uncommon term rarely resonating through elementary classrooms. However, it is a concept found in both fourth and sixth grade Arizona science standards. As issues involving the environment are becoming more pertinent, it is important to study and understand atmospheric processes along with fulfilling the standards for each grade level. This thesis project teaches the practical skills of weather map reading and weather forecasting through the creation and execution of an after school lesson with the aide of seven teen assistants.
ContributorsChoulet, Shayna (Author) / Walters, Debra (Thesis director) / Oliver, Jill (Committee member) / Balling, Robert (Committee member) / Barrett, The Honors College (Contributor) / College of Liberal Arts and Sciences (Contributor)
Created2012-12