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- Genre: Masters Thesis
Description
Microbially induced calcium carbonate precipitation (MICP) is attracting increasing attention as a sustainable means of soil improvement. While there are several possible MICP mechanisms, microbial denitrification has the potential to become one of the preferred methods for MICP because complete denitrification does not produce toxic byproducts, readily occurs under anoxic conditions, and potentially has a greater carbonate yield per mole of organic electron donor than other MICP processes. Denitrification may be preferable to ureolytic hydrolysis, the MICP process explored most extensively to date, as the byproduct of denitrification is benign nitrogen gas, while the chemical pathways involved in hydrolytic ureolysis processes produce undesirable and potentially toxic byproducts such as ammonium (NH4+). This thesis focuses on bacterial denitrification and presents preliminary results of bench-scale laboratory experiments on denitrification as a candidate calcium carbonate precipitation mechanism. The bench-scale bioreactor and column tests, conducted using the facultative anaerobic bacterium Pseudomonas denitrificans, show that calcite can be precipitated from calcium-rich pore water using denitrification. Experiments also explore the potential for reducing environmental impacts and lowering costs associated with denitrification by reducing the total dissolved solids in the reactors and columns, optimizing the chemical matrix, and addressing the loss of free calcium in the form of calcium phosphate precipitate from the pore fluid. The potential for using MICP to sequester radionuclides and metal contaminants that are migrating in groundwater is also investigated. In the sequestration process, divalent cations and radionuclides are incorporated into the calcite structure via substitution, forming low-strontium calcium carbonate minerals that resist dissolution at a level similar to that of calcite. Work by others using the bacterium Sporosarcina pasteurii has suggested that in-situ sequestration of radionuclides and metal contaminants can be achieved through MICP via hydrolytic ureolysis. MICP through bacterial denitrification seems particularly promising as a means for sequestering radionuclides and metal contaminants in anoxic environments due to the anaerobic nature of the process and the ubiquity of denitrifying bacteria in the subsurface.
ContributorsHamdan, Nasser (Author) / Kavazanjian, Edward (Thesis advisor) / Rittmann, Bruce E. (Thesis advisor) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2013
Description
In the Rare-earth-Tri-telluride family, (RTe3s) [R=La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Ho, Tm] the emergence of Charge Density Waves, (CDW) has been under investigation for a long time due to broadly tunable properties by either chemical substitution or pressure application. These quasi 2D Layered materials RTe3s undergo Fermi Surface Nesting leading to CDW instability. CDWs are electronic instabilities found in low-dimensional materials with highly anisotropic electronic structures. Since the CDW is predominantly driven by Fermi-surface (FS) nesting, it is especially sensitive to pressure-induced changes in the electronic structure. The FS of RTe3s is a function of p-orbitals of Tellurium atoms, which are arranged in two adjacent planes in the crystal structure. Although the FS and electronic structure possess a nearly four-fold symmetry, RTe3s form an incommensurate CDW.This dissertation is structured as follows: Chapter 1 includes basic ideas of Quantum materials, followed by an introduction to CDW and RTe3s. In Chapter 2, there are fundamentals of crystal growth by Chemical Vapor Transport, including various precursors, transport agent, temperature gradient, and rate of the reaction. After the growth, the crystals were confirmed for lattice vibrations by Raman, for composition by Energy Dispersive Spectroscopy; crystal structure and orientation were confirmed by X-ray Diffraction; magnetic ordering was established by Vibrating sample measurement. Detailed CDW study was done on various RTe3s by Raman spectroscopy. The basic mechanism and instrumentations used in these characterizations are explained in Chapter 3. Chapter 4 includes experimental data for crystal growth and results of these characterizations for Parent RTe3s. Chapter 5 includes fundamental insights on Cationic alloying of RTe3s, along with one alloy system’s crystal growth and characterization. This work tries to explain the behavior of CDW by a Temperature-dependent Raman study of RTe3s established the CDW transition temperature accompanied by Phonon softening; Angle-resolved Raman data confirming the nearly four-fold symmetry; thickness-dependent Raman spectroscopy resulting in the conclusion that as thickness decreases CDW transition temperature increases. Also, CDW transition is analyzed as a function of alloying.
ContributorsAttarde, Yashika (Author) / Tongay, Sefaattin (Thesis advisor) / Botana, Antia (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
Description
Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are crucial nutrients for autotrophic and heterotrophic microbial life, respectively, in hydrothermal systems. Biogeochemical processes that control amounts of DIC and DOC in Yellowstone hot springs can be investigated by measuring carbon abundances and respective isotopic values. A decade and a half of field work in 10 regions within Yellowstone National Park and subsequent geochemical lab analyses reveal that sulfate-dominant acidic regions have high DOC (Up to 57 ppm C) and lower DIC (up to 50 ppm C) compared to neutral-chloride regions with low DOC (< 2 ppm C) and higher DIC (up to 100 ppm C). Abundances and isotopic data suggest that sedimentary rock erosion by acidic hydrothermal fluids, fresh snow-derived meteoric water, and exogenous carbon input allowed by local topography may affect DOC levels. Evaluating the isotopic compositions of DIC and DOC in hydrothermal fluids gives insight on the geology and microbial life in the subsurface between different regions. DIC δ13C values range from -4‰ to +5‰ at pH 5-9 and from -10‰ to +3‰ at pH 2-5 with several springs lower than -10‰. DOC δ13C values parkwide range from -10‰ to -30‰. Within this range, neutral-chloride regions in the Lower Geyser Basin have lighter isotopes than sulfate-dominant acidic regions. In hot springs with elevated levels of DOC, the range only varies between -20‰ and -26‰ which may be caused by local exogenous organic matter runoff. Combining other geochemical measurements, such as differences in chloride and sulfate concentrations, demonstrates that some regions contain mixtures of multiple fluids moving through the complex hydrological system in the subsurface. The mixing of these fluids may account for increased levels of DOC in meteoric sulfate-dominant acidic regions. Ultimately, the foundational values of dissolved carbon and their isotopic composition is provided in a parkwide study, so results can be combined with future studies that apply different sequencing analyses to understand specific biogeochemical cycling and microbial communities that occur in individual hot springs.
ContributorsBarnes, Tanner (Author) / Shock, Everett (Thesis advisor) / Meyer-Dombard, D'Arcy (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2023
Description
Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging. Moreover, there is no fixed framework to identify the doping concentration, which impedes their process integration for future commercialization. This work utilizes the Neutron Transmutation Doping technique to control the doping uniformly and precisely in TMDCs. Rhenium and Tin dopants are introduced in Tungsten- and Indium-based Chalcogenides, respectively. Fine-tuning over 0.001% doping level is achieved. Precise analytical techniques such as Gamma spectroscopy and Secondary Ion Mass Spectrometry are used to quantify ultra-low doping levels ranging from 0.005-0.01% with minimal error. Dopants in 2D TMDCs often exhibit a broad stokes-shifted emission, with high linewidths, due to extrinsic effects such as substrate disorder and surface adsorbates. A well-defined bound exciton emission induced by Rhenium dopants in monolayer WSe2 and WS2 at liquid nitrogen temperatures is reported along with specific annealing regimes to minimize the defects induced in the Neutron Transmutation process. This work demonstrates a framework for Neutron Doping in 2D materials, which can be a scalable process for controlling doping and doping-induced effects in 2D materials.
ContributorsLakhavade, Sushant Sambhaji (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2023
Description
In the past decade, 2D materials especially transition metal dichalcogenides (TMDc), have been studied extensively for their remarkable optical and electrical properties arising from their reduced dimensionality. A new class of materials developed based on 2D TMDc that has gained great interest in recent years is Janus crystals. In contrast to TMDc, Janus monolayer consists of two different chalcogen atomic layers between which the transition metal layer is sandwiched. This structural asymmetry causes strain buildup or a vertically oriented electric field to form within the monolayer. The presence of strain brings questions about the materials' synthesis approach, particularly when strain begins to accumulate and whether it causes defects within monolayers.The initial research demonstrated that Janus materials could be synthesized at high temperatures inside a chemical vapor deposition (CVD) furnace. Recently, a new method (selective epitaxy atomic replacement - SEAR) for plasma-based room temperature Janus crystal synthesis was proposed. In this method etching and replacing top layer chalcogen atoms of the TMDc monolayer happens with reactive hydrogen and sulfur radicals. Based on Raman and photoluminescence studies, the SEAR method produces high-quality Janus materials. Another method used to create Janus materials was the pulsed laser deposition (PLD) technique, which utilizes the interaction of sulfur/selenium plume with monolayer to replace the top chalcogen atomic layer in a single step.
The goal of this analysis is to characterize microscale defects that appear in 2D Janus materials after they are synthesized using SEAR and PLD techniques. Various microscopic techniques were used for this purpose, as well as to understand the
mechanism of defect formation. The main mechanism of defect formation was proposed to be strain release phenomena. Furthermore, different chalcogen atom positions within the monolayer result in different types of defects, such as the appearance of cracks or wrinkles across monolayers. In addition to investigating sample topography, Kelvin probe force microscopy (KPFM) was used to examine its electrical properties to see if the formation of defects impacts work function. Further study directions have been suggested for identifying and characterizing defects and their formation mechanism in the Janus crystals to understand their fundamental properties.
ContributorsSinha, Shantanu (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2022
Description
Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides (TMDs). These 2D materials were shown to have highly controllable bandgaps which can be controlled by alloying. Only a small number of TMDs and monochalcogenides have been alloyed, though, because alloying compromised the material's Van der Waals (Vdw) property and the stability of the host crystal lattice phase. Phase transition in 2D materials is an interesting phenomenon where work has been done only on few TMDs namely MoTe2, MoS2, TaS2 etc.In order to change the band gaps and move them towards the UV (ultraviolet) and IR (infrared) regions, this work has developed new 2D alloys in InSe by alloying them with S and Te at 10% increasing concentrations. As the concentration of the chalcogens (S and Te) increased past a certain point, a structural phase transition in the alloys was observed. However, pinpointing the exact concentration for phase change and inducing phase change using external stimuli will be a thing of the future. The resulting changes in the crystal structure and band gap were characterized using some basic characterization techniques like scanning electron microscopy (SEM), X-ray Diffraction (XRD), Raman and photoluminescence spectroscopy.
ContributorsYarra, Anvesh Sai (Author) / Tongay, Sefaattin (Thesis advisor) / Yang, Sui (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2022
Description
Metal-Oxide-Semiconductor (MOS) is essential to modern VLSI devices. In the past decades, a wealth of literature has been created to understand the impact of the radiation-induced charges on the devices, i.e., the creation of electron-hole pairs in the oxide layer which is the most sensitive part of MOS structure to the radiation effect. In this work, both MOS and MNOS devices were fabricated at ASU NanoFab to study the total ionizing dose effect using capacitance-voltage (C-V) electrical characterization by observing the direction and amounts of the shift in C-V curves and electron holography observation to directly image the charge buildup at the irradiated oxide film of the oxide-only MOS device.C-V measurements revealed the C-V curves shifted to the left after irradiation (with a positive bias applied) because of the net positive charges trapped at the oxide layer for the oxide-only sample. On the other hand, for nitride/oxide samples with positive biased during irradiation, the C-V curve shifted to the right due to the net negative charges trapped at the oxide layer. It was also observed that the C-V curve has less shift in voltage for MNOS than MOS devices after irradiation due to the less charge buildup after irradiation.
Off-axis electron holography was performed to map the charge distribution across the MOSCAP sample. Compared with both pre-and post-irradiated samples, a larger potential drop at the Si/SiO2 was noticed in post-irradiation samples, which indicates the presence of greater amounts of positive charges that buildup the Si/SiO2 interface after the TID exposure.
TCAD modeling was used to extract the density of charges accumulated near the SiO2/Si and SiO2/ Metal interface by matching the simulation results to the potential data from holography. The increase of near-interface positive charges in post-irradiated samples is consistent with the C-V results.
ContributorsChang, Ching Tao (Author) / Barnaby, Hugh (Thesis advisor) / Holbert, Keith (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023
Description
Vanadium-dioxide-based devices show great switchability in their optical properties due to its dramatic thermochromic phase transition from insulator to metal, but generally have concerns due to its relatively high transition temperature at 68 °C. Doping the vanadium dioxide with tungsten has been shown to reduce its transition temperature at the cost lower optical property differences between its insulating and metallic phases. A recipe is developed through parametric experimentation to fabricate tungsten-doped vanadium dioxide consisting of a novel dual target co-sputtering deposition, a furnace oxidation process, and a post-oxidation annealing process. The transmittance spectra of the resulting films are measured via Fourier-transform infrared spectroscopy at different temperatures to confirm the lowered transition temperature and analyze their thermal-optical hysteresis behavior through the transition temperature range. Afterwards, the optical properties of undoped sputtered vanadium films are modeled and effective medium theory is used to explain the effect of tungsten dopants on the observed transmittance decrease of doped vanadium dioxide. The optical modeling is used to predict the performance of tungsten-doped vanadium dioxide devices, in particular a Fabry-Perot infrared emitter and a nanophotonic infrared transmission filter. Both devices show great promise in their optical properties despite a slight performance decrease from the tungsten doping. These results serve to illustrate the excellent performance of the co-sputtered tungsten-doped vanadium dioxide films.
ContributorsChao, Jeremy (Author) / Wang, Liping (Thesis advisor) / Wang, Robert (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2022
Description
Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into these minerals.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
ContributorsChen, Xinming (Author) / Anbar, Ariel (Thesis advisor) / Herckes, Pierre (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2015
Description
This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3).
Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
ContributorsPant, Anupum (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry Lynn (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016