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- Genre: Doctoral Dissertation
Description
The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes a question of understanding biomolecular dynamics that span a variety of timescales (from electronic rearrangements in the femtoseconds to side-chain alteration in the microseconds and more). This dissertation deals with the study of biomolecular dynamics in the ultrafast timescales (fs-ns) using electron and X-ray probes in both time and frequency domains.
It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided.
Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution.
It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided.
Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Rez, Peter (Committee member) / Alford, Terry (Committee member) / Weierstall, Uwe (Committee member) / Kirian, Richard (Committee member) / Arizona State University (Publisher)
Created2016
Description
Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.
ContributorsNorton, Tyler (Author) / Lin, Jerry Y.S. (Thesis advisor) / Alford, Terry (Committee member) / Lind, Mary Laura (Committee member) / Smith, David (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2013
Description
I studied the properties of novel Co2FeAl0.5Si0.5 (CFAS), ZnGeAs2, and FeS2 (pyrite) thin films for microelectronic applications ranging from spintronic to photovoltaic. CFAS is a half metal with theoretical spin polarization of 100%. I investigated its potential as a spin injector, for spintronic applications, by studying the critical steps involved in the injection of spin polarized electron populations from tunnel junctions containing CFAS electrodes. Epitaxial CFAS thin films with L21 structure and saturation magnetizations of over 1200 emu/cm3 were produced by optimization of the sputtering growth conditions. Point contact Andreev reflection measurements show that the spin polarization at the CFAS electrode surface exceeds 70%. Analyses of the electrical properties of tunnel junctions with a superconducting Pb counter-electrode indicate that transport through native Al oxide barriers is mostly from direct tunneling, while that through the native CFAS oxide barriers is not. ZnGeAs2 is a semiconductor comprised of only inexpensive and earth-abundant elements. The electronic structure and defect properties are similar in many ways to GaAs. Thus, in theory, efficient solar cells could be made with ZnGeAs2 if similar quality material to that of GaAs could be produced. To understand the thermochemistry and determine the rate limiting steps of ZnGeAs2 thin-film synthesis, the (a) thermal decomposition rate and (b) elemental composition and deposition rate of films were measured. It is concluded that the ZnGeAs2 thin film synthesis is a metastable process with an activation energy of 1.08±0.05 eV for the kinetically-limited decomposition rate and an evaporation coefficient of ~10-3. The thermochemical analysis presented here can be used to predict optimal conditions of ZnGeAs2 physical vapor deposition and thermal processing. Pyrite (FeS2) is another semiconductor that has tremendous potential for use in photovoltaic applications if high quality materials could be made. Here, I present the layer-by-layer growth of single-phase pyrite thin-films on heated substrates using sequential evaporation of Fe under high-vacuum followed by sulfidation at S pressures between 1 mTorr and 1 Torr. High-resolution transmission electron microscopy reveals high-quality, defect-free pyrite grains were produces by this method. It is demonstrated that epitaxial pyrite layer was produced on natural pyrite substrates with this method.
ContributorsVahidi, Mahmoud (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry (Committee member) / Singh, Rakesh (Committee member) / Chen, Tingyong (Committee member) / Arizona State University (Publisher)
Created2013
Description
Silicon carbide (SiC), long touted as a material that can satisfy the specific property requirements for high temperature and high power applications, was studied quantitatively using various techniques. The electronic band structure of 4H SiC is examined in the first half of this dissertation. A brief introduction to band structure calculations, with particular emphasis on the empirical pseudopotential method, is given as a foundation for the subsequent work. Next, the crystal pseudopotential for 4H SiC is derived in detail, and a novel approach using a genetic algorithm search routine is employed to find the fitting parameters needed to generate the band structure. Using this technique, the band structure is fitted to experimentally measured energy band gaps giving an indirect band gap energy of 3.28 eV, and direct f¡, M, K and L energy transitions of 6.30, 4.42, 7.90 and 6.03 eV, respectively. The generated result is also shown to give effective mass values of mMf¡*=0.66m0, mMK*=0.31m0, mML*=0.34m0, in close agreement with experimental results. The second half of this dissertation discusses computational work in finding the electron Hall mobility and Hall scattering factor for 6H SiC. This disscussion begins with an introductory chapter that gives background on how scattering rates are dervied and the specific expressions for important mechanisms. The next chapter discusses mobility calculations for 6H SiC in particular, beginnning with Rode's method to solve the Boltzmann transport equation. Using this method and the transition rates of the previous chapter, an acoustic deformation potential DA value of 5.5 eV, an inter-valley phonon deformation potential Dif value of 1.25~1011 eV/m and inter-valley phonon energy ℏfÖif of 65 meV that simultaneously fit experimental data on electron Hall mobility and Hall scattering factor was found.
ContributorsNg, Garrick (Author) / Schroder, Dieter K. (Thesis advisor) / Vasileska, Dragica (Committee member) / Skromme, Brian (Committee member) / Alford, Terry (Committee member) / Marinella, Matthew (Committee member) / Arizona State University (Publisher)
Created2010
Description
Transparent conductive oxides (TCOs) are used as electrodes for a number of optoelectronic devices including solar cells. Because of its superior transparent and conductive properties, indium (In) tin (Sn) oxide (ITO) has long been at the forefront for TCO research activities and high-volume product applications. However, given the limited supply of In and potential toxicity of Sn-based compounds, attention has shifted to alternative TCOs like ZnO doped with group-III elements such as Ga and Al. Employing a variety of deposition techniques, many research groups are striving to achieve resistivities below 1E-4 ohm-cm with transmittance approaching the theoretical limit over a wide spectral range. In this work, Ga-doped ZnO is deposited using pulsed laser deposition (PLD). Material properties of the films are characterized using a number of techniques. For deposition in oxygen at pressures >1 mTorr, post-deposition annealing in forming gas (FG) is required to improve conductivity. At these higher oxygen pressures, thermodynamic analysis coupled with a study using the Hall effect measurements and photoluminescence spectroscopy suggest that conductivity is limited by oxygen-related acceptor-like defects in the grains that compensate donors, effectively reducing the net carrier concentration and creating scattering centers that reduce electron mobility. Oxygen is also responsible for further suppression of conductivity by forming insulative metal oxide regions at the grain edges and oxygen-related electron traps at the grain boundaries. The hydrogen component in the FG is thought to passivate the intra-grain acceptor-like defects and improve carrier transport across these grain boundaries. Given this deleterious effect of oxygen on conductivity, depositions are performed in pure argon (Ar), i.e., the only oxygen species in the growth ambient are those ejected directly from the PLD solid source target. Ga-doped ZnO deposited in Ar at 200 °C and 10 mTorr have resistivities of 1.8E-4 ohm-cm without the need for post deposition annealing. Average transmittance of the Ga-doped films is 93% over the visible and near infrared (IR) spectral regions, but free carrier absorption is a limiting factor further into the IR. After annealing in FG at 500 °C, a 300 nm Ar film has a Haacke figure of merit of 6.61E-2 sq. ohm.
ContributorsScott, Robin Charis (Author) / Zhang, Yong Hang (Thesis advisor) / Alford, Terry (Committee member) / Krause, Stephen (Committee member) / Leedy, Kevin (Committee member) / Arizona State University (Publisher)
Created2011
Description
Programmable Metallization Cell (PMC) is a resistance-switching device based on migration of nanoscale quantities of cations in a solid electrolyte and formation of a conducting electrodeposit by the reductions of these cations. This dissertation presents electrical characterization results on Cu-SiO2 based PMC devices, which due to the na- ture of materials can be easily integrated into the current Complimentary metal oxide semiconductor (CMOS) process line. Device structures representing individual mem- ory cells based on W bottom electrode and n-type Si bottom electrode were fabricated for characterization. For the W bottom electrode based devices, switching was ob- served for voltages in the range of 500mV and current value as low as 100 nA showing the electrochemical nature and low power potential. The ON state showed a direct de- pendence on the programming current, showing the possibility of multi-bit storage in a single cell. Room temperature retention was demonstrated in excess of 105 seconds and endurance to approximately 107 cycles. Switching was observed for microsecond duration 3 V amplitude pulses. Material characterization results from Raman, X-ray diffraction, Rutherford backscattering and Secondary-ion mass spectroscopy analysis shows the influence of processing conditions on the Cu concentration within the film and also the presence of Cu as free atoms. The results seemed to indicate stress-induced void formation in the SiO2 matrix as the driving mechanism for Cu diffusion into the SiO2 film. Cu/SiO2
Si based PMC devices were characterized and were shown to have inherent isolation characteristics, proving the feasibility of such a structure for a passive array. The inherent isolation property simplifies fabrication by avoiding the need for a separate diode element in an array. The isolation characteristics were studied mainly in terms of the leakage current. The nature of the diode interface was further studied by extracting a barrier potential which shows it can be approximated to a Cu-nSi metal semiconductor Schottky diode.
Si based PMC devices were characterized and were shown to have inherent isolation characteristics, proving the feasibility of such a structure for a passive array. The inherent isolation property simplifies fabrication by avoiding the need for a separate diode element in an array. The isolation characteristics were studied mainly in terms of the leakage current. The nature of the diode interface was further studied by extracting a barrier potential which shows it can be approximated to a Cu-nSi metal semiconductor Schottky diode.
ContributorsPuthenthermadam, Sarath (Author) / Kozicki, Michael N (Thesis advisor) / Diaz, Rodolfo (Committee member) / Schroder, Dieter K. (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2011
Description
Over the past three decades, significant progress in the development of organic light-emitting diodes (OLEDs) has been achieved, enabling OLEDs to become a main component in state-of-the-art displays and next generation solid-state lighting. As this technology advances, it is highly desirable to further improve the device efficiency and operational stability to drive the success of OLEDs in future display and lighting applications. This dissertation aims at developing novel organic emitting materials covering visible and near-infrared (NIR) emissions for efficient and table OLEDs. Firstly, a series of tetradentate Pd(II) complexes, which have attractive phosphorescent aggregate emission performance especially at high brightness level in device settings, have been developed. The luminescent lifetime of Pd(II) complex aggregates was demonstrated to be shorter than 1 μs with a close-to-unity photoluminescence quantum yield. Moreover, a systematic study regarding structure-property relationship was conducted on four tetradentate Pd(II) complexes, i.e., Pd3O3, Pd3O8-P, Pd3O8-Py2, and Pd3O8-Py5, featuring aggregate emission. As a result, an extremely efficient and stable OLED device utilizing Pd3O8-Py5 was achieved. It demonstrated a peak external quantum efficiency (EQE) of 37.3% with a reduced efficiency roll-off retaining a high EQE of 32.5% at 10000 cd m-2, and an estimated LT95 lifetime (time to 95% of the initial luminance) of 48246 h at 1000 cd m-2. Secondly, there is an increasing demand for NIR OLEDs with emission spectra beyond 900 nm to expand their applications in biometric authentication, night vision display, and telecommunication, etc. A stable and efficient NIR Pt(II) porphyrin complex named PtTPTNP-F8 was developed, and exhibited an electroluminescent spectrum at 920 nm. By carefully choosing the host materials, an PtTPTNP-F8 based NIR OLED achieved a EQE of 1.9%. Furthermore, an PtTPTNP-F8 OLED fabricated in a stable device structure demonstrated extraordinary operational stability with LT99 of >1000 h at 20 mA cm-2. Lastly, a series of imidazole-based blue Pt(II) complexes were developed and studied. Results indicated that structural modification of ligand molecules effectively tuned the emission spectral wavelength and bandwidth. Two blue complexes, i.e., Pt2O2 P2M and Pt2O2-PPy5-M, emitting at 472 and 476 nm respectively, exhibited narrow-band emission spectra with a full width at half maximum of 16 nm.
ContributorsCao, Linyu (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
Description
Wide Bandgap (WBG) semiconductor materials are shaping day-to-day technologyby introducing powerful and more energy responsible devices. These materials have
opened the door for building basic semiconductor devices which are superior in terms of
handling high voltages, high currents, power, and temperature which is not possible using
conventional silicon technology. As the research continues in the field of WBG based
devices, there is a potential chance that the power electronics industry can save billions of
dollars deploying energy-efficient circuits in high power conversion electronics. Diamond,
silicon carbide and gallium nitride are the top three contenders among which diamond can
significantly outmatch others in a variety of properties. However, diamond technology is
still in its early phase of development and there are challenges involved in many aspects of
processing a successful integrated circuit. The work done in this research addresses three
major aspects of problems related to diamond technology. In the first part, the applicability
of compact modeling and Technology Computer-Aided Design (TCAD) modeling
technique for diamond Schottky p-i-n diodes has been demonstrated. The compact model
accurately predicts AC, DC and nonlinear behavior of the diode required for fast circuit
simulation. Secondly, achieving low resistance ohmic contact onto n-type diamond is one
of the major issues that is still an open research problem as it determines the performance
of high-power RF circuits and switching losses in power converters circuits. So, another
portion of this thesis demonstrates the achievement of very low resistance ohmic contact
(~ 10-4 Ω⋅cm2) onto n-type diamond using nano crystalline carbon interface layer. Using
the developed TCAD and compact models for low resistance contacts, circuit level
predictions show improvements in RF performance. Lastly, an initial study of breakdown
characteristics of diamond and cubic boron nitride heterostructure is presented. This study
serves as a first step for making future transistors using diamond and cubic boron nitride –
a very less explored material system in literature yet promising for extreme circuit
applications involving high power and temperature.
ContributorsJHA, VISHAL (Author) / Thornton, Trevor (Thesis advisor) / Goodnick, Stephen (Committee member) / Nemanich, Robert (Committee member) / Alford, Terry (Committee member) / Hoque, Mazhar (Committee member) / Arizona State University (Publisher)
Created2023
Description
Perovskite solar cells are one of the rising stars in the solar cell industry. This thesis explores several approaches to enhance the properties of the perovskite layer and the solar cell devices in which they operate. They include studies of different antisolvent additives during spin coating of triple cation perovskites, the use of surfactants to improve the quality of perovskite film microstructures, the applicability of a new fabrication process, and the value of post-deposition thermal and chemical annealing processes.This thesis experimentally analyzes different antisolvents, viz., ethyl acetate, isopropyl alcohol, toluene, and chlorobenzene. It focuses on the antisolvent-assisted crystallization method to achieve homogenous nucleation of the perovskite film. Of all the antisolvents, ethyl acetate-treated films gave the best-performing device, achieving a power conversion efficiency of 15.5%.
This thesis also analyzes the effects of mixed antisolvents on the qualities of triple-cation perovskites. Different solution concentrations of chlorobenzene in ethyl acetate and isopropyl alcohol in ethyl acetate are optimized for optimal supersaturation to achieve enlarged perovskite grains. Evaluations are discussed in the context of solution polarity and boiling point of the antisolvents, where 25% chlorobenzene in ethyl acetate antisolvent mixture shows the best film properties.
Another study discusses a new fabrication process called electrical field-assisted direct ink deposition for large-scale printing of perovskite solar cells. This process involves the formation of nanodroplets under an electrical field deposited onto ITO/glass substrates. As a result, smooth Poly (3,4-ethylene dioxythiophene) polystyrene sulfonate layers are
ii
produced with an average effective electrical resistivity of 4.15104 0.26 -m compared to that of spin-coated films.
A successive chapter discusses the studies of the electrical field-assisted direct ink deposition of the photoactive CH3NH3PbI2 (MAPbI3) layer. Its focus is on the post-deposition chemical annealing of the MAPbI3 films in methylamine gas, termed as methylamine gas-assisted healing and growth of perovskite films. This treatment improved the smoothness, reduced porosity, increased density, and generated more uniform grain sizes. Moreover, it improved the inter-grain boundary contacts by eliminating secondary, fine-grained boundary structures. Mechanisms behind the initial liquefaction of the MAPbI3 film's subsequent re-solidification are discussed.
ContributorsGogoi, Banashree (Author) / Alford, Terry (Thesis advisor) / Petuskey, William (Thesis advisor) / Gould, Ian (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2023
Description
Solid-state and non-equilibrium processings are of great interest to researchers due to their ability to control and refine bulk and/or surface microstructure of metallic alloys and push them to surpass their conventional properties limit. In this dissertation, solid-state processing i.e., Shear Assisted Processing and Extrusion (ShAPE), and non-equilibrium processes i.e., surface mechanical attrition (SMAT) and additive manufacturing (AM) techniques were used to process the magnesium and aluminum alloys respectively. A synergistic investigation of processing-induced microstructural modification and its effect on corrosion resistance was performed using various ex-situ, quasi in-situ, and in-situ electrochemical, microscopy, and spectroscopy characterization techniques. To evaluate the effect of the same processing condition on a range of microstructures, a variety of magnesium alloys such as AZ31B, Mg-3Si, ZK60, and Pure Mg were processed using a novel solid-state processing method, namely ShAPE. It induced a significant grain refinement, homogenized distribution of second phases, and low residual strain in AZ31B alloy, which contributed toward a noble breakdown potential, stable protective film, and hence better corrosion resistance compared to the parent extruded counterpart. However, with variations in composition, volume fraction, and distribution of second phases with Mg-3Si and ZK60 magnesium alloy an opposite response was inferred indicating a strong dependence of corrosion on underlying microstructure compared to a processing condition. Non-equilibrium processes, i.e. SMAT and AM were utilized to process high-strength 7xxx series aluminum alloys. Continuous high energy impacts of hard balls in room temperature (RT SMAT) and liquid nitrogen (LN2 SMAT) flow environment generated a gradient nanocrystalline surface layer with the dissolution of inherent second phase and precipitation of new phases in aluminum 7075 alloys. RT SMAT showed a reduced anodic dissolution rate and improved film resistance, which was attributed to the thicker and composite oxide layer along with new nanoscale precipitates. Lastly, reactive AM was used to process aluminum 7075 and 7050 alloys which resulted in a refined and textureless microstructure. A reduction in corrosion resistance was observed with precipitation of excessive reactive particles (Ti and B4C) in AM alloys compared to wrought counterparts.
ContributorsBeura, Vikrant Kumar (Author) / Solanki, Kiran N (Thesis advisor) / Peralta, Pedro (Committee member) / Alford, Terry (Committee member) / Ankit, Kumar (Committee member) / Joshi, Vineet V (Committee member) / Arizona State University (Publisher)
Created2022