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Modifying the organic/electrode interface in Organic Solar Cells (OSCs) and improving the efficiency of solution-processed phosphorescent Organic Light-Emitting Diodes (OLEDs)

Description: Organic semiconductors devices, such as, organic solar cells (OSCs), organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs) have drawn increasing interest in recent decades. As organic materials are flexible, light weight, and potentially low-cost, organic semiconductor devices are considered to be an alternative to their inorganic counterparts. This dissertation will focus mainly on OSCs and OLEDs. As a clean and renewable energy source, the development of OSCs is very promising. Cells with 9.2% power conversion efficiency (PCE) were reported this year, compared to < 8% two years ago. OSCs belong to the so-called third generation solar cells and are still under development. While OLEDs are a more mature and better studied field, with commercial products already launched in the market, there are still several key issues: (1) the cost of OSCs/OLEDs is still high, largely due to the costly manufacturing processes; (2) the efficiency of OSCs/OLEDs needs to be improved; (3) the lifetime of OSCs/OLEDs is not sufficient compared to their inorganic counterparts; (4) the physics models of the behavior of the devices are not satisfactory. All these limitations invoke the demand for new organic materials, improved device architectures, low-cost fabrication methods, and better understanding of device physics. For OSCs, we attempted to improve the PCE by modifying the interlayer between active layer/metal. We found that ethylene glycol (EG) treated poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) improves hole collection at the metal/polymer interface, furthermore it also affects the growth of the poly(3- hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) blends, making the phase segregation more favorable for charge collection. We then studied organic/inorganic tandem cells. We also investigated the effect of a thin LiF layer on the hole-collection of copper phthalocyanine (CuPc)/C70-based small molecular OSCs. A thin LiF layer serves typically as the electron injection layer in OLEDs and electron collection interlayer ...
Date: April 27, 2012
Creator: Xiao, Teng
Partner: UNT Libraries Government Documents Department

Developments in enzyme immobilization and near-infrared Raman spectroscopy with downstream renewable energy applications

Description: This dissertation focuses on techniques for (1) increasing ethanol yields from saccharification and fermentation of cellulose using immobilized cellulase, and (2) the characterization and classification of lignocellulosic feedstocks, and quantification of useful parameters such as the syringyl/guaiacyl (S/G) lignin monomer content using 1064 nm dispersive multichannel Raman spectroscopy and chemometrics.
Date: August 27, 2012
Creator: Lupoi, Jason
Partner: UNT Libraries Government Documents Department

Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

Description: This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.
Date: July 27, 2012
Creator: Ebert, Christopher Hysjulien
Partner: UNT Libraries Government Documents Department

Strange-Particle Production by 1170-MeV/c pi- Mesons

Description: Production of {Lambda} + K{sup 0}, {Sigma}{sup 0} + K{sup 0}, and {Sigma}{sup -} + K{sup +} by 1170-MeV/c {pi}{sup -} mesons has been studied in the Lawrence Radiation Laboratory 72-inch hydrogen bubble chamber, Cross sections, angular distributions, and polarizations are presented. The polarization of the {Sigma}{sup 0} is determined at four center-of-mass angles and found to be small everywhere. Based on published results for the reaction {pi}{sup +} + p {yields} {Sigma}{sup +}, K{sup +}, a comparison of the polarizations of {Sigma}{sup +}, {Sigma}{sup -}, and {Sigma}{sup 0} is made from the charge-independence triangle. A conclusion is reached that the {Sigma}{sup -} polarization should be large, and that the {Sigma}{sup -} and {Sigma}{sup +} polarizations should be opposite in sign.
Date: May 27, 1963
Creator: Anderson, Jared Arnold
Partner: UNT Libraries Government Documents Department

SAMPLING AND MASS SPECTROMETRY APPROACHES FOR THE DETECTION OF DRUGS AND FOREIGN CONTAMINANTS IN BREATH FOR HOMELAND SECURITY APPLICATIONS

Description: Homeland security relies heavily on analytical chemistry to identify suspicious materials and persons. Traditionally this role has focused on attribution, determining the type and origin of an explosive, for example. But as technology advances, analytical chemistry can and will play an important role in the prevention and preemption of terrorist attacks. More sensitive and selective detection techniques can allow suspicious materials and persons to be identified even before a final destructive product is made. The work presented herein focuses on the use of commercial and novel detection techniques for application to the prevention of terrorist activities. Although drugs are not commonly thought of when discussing terrorism, narcoterrorism has become a significant threat in the 21st century. The role of the drug trade in the funding of terrorist groups is prevalent; thus, reducing the trafficking of illegal drugs can play a role in the prevention of terrorism by cutting off much needed funding. To do so, sensitive, specific, and robust analytical equipment is needed to quickly identify a suspected drug sample no matter what matrix it is in. Single Particle Aerosol Mass Spectrometry (SPAMS) is a novel technique that has previously been applied to biological and chemical detection. The current work applies SPAMS to drug analysis, identifying the active ingredients in single component, multi-component, and multi-tablet drug samples in a relatively non-destructive manner. In order to do so, a sampling apparatus was created to allow particle generation from drug tablets with on-line introduction to the SPAMS instrument. Rules trees were developed to automate the identification of drug samples on a single particle basis. A novel analytical scheme was also developed to identify suspect individuals based on chemical signatures in human breath. Human breath was sampled using an RTube{trademark} and the trace volatile organic compounds (VOCs) were preconcentrated using solid phase microextraction ...
Date: January 27, 2009
Creator: Martin, A N
Partner: UNT Libraries Government Documents Department

Soft X-ray emission spectroscopy of liquids and lithium batterymaterials

Description: Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite {pi}-bands have been observed. Transfer of electrons in to the 3d states of transition metal oxides upon lithiation have been studied, through low energy excitations as dd- and charge transfer-excitations. A SEI was detected on cycled graphite electrodes. By the use of selective excitation different carbon sites were probed in the SEI. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell, to separate the liquid from the vacuum in the experimental chamber. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and ...
Date: October 27, 2004
Creator: Augustsson, Andreas
Partner: UNT Libraries Government Documents Department

Scalable Performance Measurement and Analysis

Description: Concurrency levels in large-scale, distributed-memory supercomputers are rising exponentially. Modern machines may contain 100,000 or more microprocessor cores, and the largest of these, IBM's Blue Gene/L, contains over 200,000 cores. Future systems are expected to support millions of concurrent tasks. In this dissertation, we focus on efficient techniques for measuring and analyzing the performance of applications running on very large parallel machines. Tuning the performance of large-scale applications can be a subtle and time-consuming task because application developers must measure and interpret data from many independent processes. While the volume of the raw data scales linearly with the number of tasks in the running system, the number of tasks is growing exponentially, and data for even small systems quickly becomes unmanageable. Transporting performance data from so many processes over a network can perturb application performance and make measurements inaccurate, and storing such data would require a prohibitive amount of space. Moreover, even if it were stored, analyzing the data would be extremely time-consuming. In this dissertation, we present novel methods for reducing performance data volume. The first draws on multi-scale wavelet techniques from signal processing to compress systemwide, time-varying load-balance data. The second uses statistical sampling to select a small subset of running processes to generate low-volume traces. A third approach combines sampling and wavelet compression to stratify performance data adaptively at run-time and to reduce further the cost of sampled tracing. We have integrated these approaches into Libra, a toolset for scalable load-balance analysis. We present Libra and show how it can be used to analyze data from large scientific applications scalably.
Date: October 27, 2009
Creator: Gamblin, T
Partner: UNT Libraries Government Documents Department

The Effect of Oxygen Contamination on the Amorphous Structure of Thermally Sprayed Coatings of Cu47Ti33Zr11Ni8Si1

Description: this research has shown that it is possible to deposit coatings of gas atomized Cu{sub 47}Ti{sub 33}Zr{sub 11}Ni{sub 8}Si{sub 1} powders containing various levels of oxygen contamination using plasma arc spray methods. The structure of the coating was found to depend primarily on the spray environment, with an argon atmosphere producing the most amorphous samples for a given starting powder. The oxygen content of the coatings reflected the relative levels of the oxygen contamination in the starting powders. The analysis of the starting powders displayed oxygen contents ranging from 0.125-0.79 wt.%. It was shown that higher oxygen levels lead to more crystalline structure in the starting powders as determined by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). This trend was found to be true for both the starting powders and for the plasma sprayed coatings. Chemical composition for all starting powders was very close to the nominal alloy composition. Chemical changes in the coatings involved the loss of Cu in coatings where high levels of oxidation were found. Cavitation erosion testing of selected coatings showed a weak trend that coatings prepared by vacuum plasma spray (VPS) had lower damage rates, but there was no clear data to indicate which coating parameters were superior. The range of data produced from testing duplicate coating was too wide to provide a good statistical measure of cavitation erosion resistance. of interest was the fact that when coatings began to show damage from cracking, all samples of a group showed similar damage and usually the damage pattern was somewhat unique to that group of samples. Failure of the coatings was due to features inherent to plasma arc spray (PAS) coating (i.e., pores, splat boundaries, oxide inclusions) rather than the mechanical characteristics of the amorphous alloy.
Date: May 27, 2002
Creator: Besser, Matthew Frank
Partner: UNT Libraries Government Documents Department

Organusulfur Catalysis With Reduced Molybdenum Sulfides Containing the Mo6S8 Cluster

Description: Industrial synthesis of sulfur-containing organic chemicals basically focuses on the broad categories of mercaptans (thiols), alkylsulfides (thioethers), polysulfides, and thiophenes. Of the organo-sulfur compounds produced, by far the most important in terms of quantities produced is methyl mercaptan (methanethiol or MeSH), which is produced mainly for the downstream production of methionine and methanesulfonyl chloride. Higher thiols are also used in the manufacture of rubber and plastics as polymerization regulators, chain transfer agents, or initiators. Other important organosulfur chemicals are dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), both of which are used extensively for presulfiding of industrial hydroprocessing catalysts, and substituted thiophenes which are used as intermediates for production of agrochemicals, dyes, and pharmaceuticals. Thiols are produced commercially at the rate of about 10{sup 4} ton/yr from hydrogen sulfide (H{sub 2}S) and alcohols or olefins, using homogeneous free-radical synthesis, or heterogeneous catalysts based on solid acids or supported metal oxides and/or sulfides. Despite this large production rate, and the industrial importance of the organosulfur compounds, only limited research has been devoted to the development of new catalytic materials for their synthesis. Additionally, for most organosulfur catalytic reactions, only limited information exists about reaction mechanisms, active sites, adsorbed surface species, and especially the nature of the catalysts under reaction conditions.
Date: August 27, 2002
Creator: Paskach, Thomas Jay
Partner: UNT Libraries Government Documents Department

Remote Field Eddy Current Probes for the Detection of Stress Corrosion in Transmission Pipelines

Description: Magnetic flux leakage (MFL) is a technique used widely in non-destructive testing (NDT) of natural gas and petroleum transmission pipelines. This inspection method relies on magnetizing the pipe-wall in axial direction. The MFL inspection tool is equipped with an array of Hall sensors located around the circumference of the pipe, which registers the flux leakage caused by any defects present in the pipe-wall. Currently, the tool magnetizes the pipewall in axial direction making it largely insensitive to axially oriented defects. One type of defect, which is of a growing concern in the gas and petroleum industry is the stress corrosion crack (SCC). The SCCs are a result of aging, corrosion, fatigue and thermal stresses. SCCs are predominantly axially oriented and are extremely tight, which makes them impossible to be detected using current inspection technology. A possible solution to this problem is to utilize the remote field eddy current (RFEC) effect to detect axially oriented defects. The RFEC method has been widely used in industry in the inspection of tubular products. The method uses a pair of excitation and pick-up coils. The pick-up coil located in the remote field region, usually two, three pipe-diameters away from the excitation coil. With RFEC the presence of defects is detected by the disturbance in the phase of the signal measured by the pick-up coil relative to that of the excitation coil. Unlike conventional eddy current testing the RFEC method is sensitive to defects on the exterior of the inspected product, which makes it a good candidate for the development of in-line inspection technology. This work focuses on the development of non-destructive testing technique, which uses remote field eddy currents induced by rotating magnetic field (RMF). A major advantage of the RMF is that it makes possible to not only detect a defect but also ...
Date: August 27, 2002
Creator: Ivanov, Plamen Alexandroz
Partner: UNT Libraries Government Documents Department

Hydrogen Storage Properties of Lithium Aluminohydride Modified by Dopants and Mechanochemistry

Description: Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al succeeded in the re-hydrogenation of NaAlH{sub 4} below 70 atm. They achieved 4 wt.% H{sub 2} reversible capacity by doping NaAlH{sub 4} with Ti and/or Fe organo-metallic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr{sub 27}Ti{sub 9}Ni{sub 38}V{sub 5}Mn{sub 16}Cr{sub 5}, LaNi{sub 4.85}Sn{sub 0.15}, Al{sub 3}Ti, and PdCl{sub 2} were combined with LiAlH{sub 4} by ball-milling to study whether or not LiAlH{sub 4} is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH{sub 4} and Li{sub 3}AlH{sub 6} by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.
Date: June 27, 2002
Creator: Hosokawa, Ketia
Partner: UNT Libraries Government Documents Department

Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

Description: The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V{sub 2}O{sub 5}-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V{sub 2}O{sub 5}, solid solutions of Mo in V{sub 2}O{sub 5}, V{sub 9}Mo{sub 6}O{sub 40}, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO{sub 3}/(V{sub 2}O{sub 5} + MoO{sub 3}), determined by EDS analysis.
Date: May 27, 2002
Creator: Schroeder, William David
Partner: UNT Libraries Government Documents Department

Electrocatalytic Materials and Techniques for the Anodic Oxidation of Various Organic Compounds

Description: The focus of this thesis was first to characterize and improve the applicability of Fe(III) and Bi(V) doped PbO{sub 2} film electrodes for use in anodic O-transfer reactions of toxic and waste organic compounds, e.g. phenol, aniline, benzene, and naphthalene. Further, they investigated the use of alternative solution/electrode interfacial excitation techniques to enhance the performance of these electrodes for remediation and electrosynthetic applications. Finally, they have attempted to identify a less toxic metal oxide film that may hold promise for future studies in the electrocatalysis and photoelectrocatalysis of O-transfer reactions using metal oxide film electrodes.
Date: June 27, 2002
Creator: Treimer, Stephen Everett
Partner: UNT Libraries Government Documents Department

Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

Description: This thesis contains the candidate's original work on excitonic structure and energy transfer dynamics of two bacterial antenna complexes as studied using spectral hole-burning spectroscopy. The general introduction is divided into two chapters (1 and 2). Chapter 1 provides background material on photosynthesis and bacterial antenna complexes with emphasis on the two bacterial antenna systems related to the thesis research. Chapter 2 reviews the underlying principles and mechanism of persistent nonphotochemical hole-burning (NPHB) spectroscopy. Relevant energy transfer theories are also discussed. Chapters 3 and 4 are papers by the candidate that have been published. Chapter 3 describes the application of NPHB spectroscopy to the Fenna-Matthews-Olson (FMO) complex from the green sulfur bacterium Prosthecochloris aestuarii; emphasis is on determination of the low energy vibrational structure that is important for understanding the energy transfer process associated within three lowest energy Q{sub y}-states of the complex. The results are compared with those obtained earlier on the FMO complex from Chlorobium tepidum. In Chapter 4, the energy transfer dynamics of the B800 molecules of intact LH2 and B800-deficient LH2 complexes of the purple bacterium Rhodopseudomonas acidophila are compared. New insights on the additional decay channel of the B800 ring of bacteriochlorophyll{sub a} (BChl{sub a}) molecules are provided. General conclusions are given in Chapter 5. A version of the hole spectrum simulation program written by the candidate for the FMO complex study (Chapter 3) is included as an appendix. The references for each chapter are given at the end of each chapter.
Date: June 27, 2002
Creator: Matsuzaki, Satoshi
Partner: UNT Libraries Government Documents Department

Zintl cluster chemistry in the alkali-metal-gallium systems

Description: Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na{sub 10}Ga{sub 10}Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K{sub 2}Ga{sub 3} Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x} is nonstoichiometric and needs only a small amount of silver to form (x {approximately} 2--6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa{sub 3{minus}x}Au{sub x} system is also nonstoichiometric with a three-dimensional structure composed of Ga{sub 8} dodecahedra and four-bonded gallium atoms. Unlike Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x}, the RbGa{sub 3} binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary is discussed but the structure has not been completely characterized.
Date: March 27, 1998
Creator: Henning, R.
Partner: UNT Libraries Government Documents Department

Applications of electrochemically-modulated liquid chromatography (EMLC): Separations of aromatic amino acids and polycyclic aromatic hydrocarbons

Description: The research in this thesis explores the separation capabilities of a new technique termed electrochemically-modulated liquid chromatography (EMLC). The thesis begins with a general introduction section which provides a literature review of this technique as well as a brief background discussion of the two research projects in each of the next two chapters. The two papers which follow investigate the application of EMLC to the separation of a mixture of aromatic amino acids and of a mixture of polycyclic aromatic hydrocarbons (PAHs). The last section presents general conclusions and summarizes the thesis. References are compiled in the reference section of each chapter. The two papers have been removed for separate processing.
Date: March 27, 1998
Creator: Deng, L.
Partner: UNT Libraries Government Documents Department

Optical spectroscopy of strongly correlated electron systems

Description: In this thesis, both time-resolved, nonlinear optical spectroscopy and linear spectroscopy are used to investigate the interactions and dynamics of elementary excitations in strongly correlated electron systems. In the first part, we investigate the renormalization of magnetic elementary excitations in the transition metal oxide Cr{sub 2}O{sub 3}. We have created a non-equilibrium population of antiferromagnetic spin waves and characterized its dynamics, using frequency- and time-resolved optical spectroscopy of the exciton-magnon transition. We observed a time-dependent pump-probe line shape, which results from excitation induced renormalization of the spin wave band structure. We present a model that reproduces the basic characteristics of the data, in which we postulate the optical nonlinearity to be dominated by interactions with long-wavelength spin waves, and the dynamics due to spin wave thermalization. Using linear spectroscopy, coherent third-harmonic generation and pump-probe experiments, we measured the optical properties of the charge-transfer (CT) gap exciton in Sr{sub 2}CuO{sub 2}Cl{sub 2}, an undoped model compound for high-temperature superconductors. A model is developed which explains the pronounced temperature dependence and newly observed Urbach tail in the linear absorption spectrum by a strong, phonon-mediated coupling between the charge-transfer exciton and ligand field excitations of the Cu atoms. The third-order nonlinear optical susceptibility within the Cu-O plane of Sr{sub 2}CuO{sub 2}Cl{sub 2} is fully characterized in both amplitude and phase, and symmetry based conclusions are made with respect to the spatial arrangement of the underlying charge distribution. Theoretical considerations ascribe a newly reported resonance in the third-order nonlinear susceptibility at 0.7 eV to a three-photon transition from the ground state to the charge-transfer exciton. An even parity intermediate state of Cudd character, is found to contribute to the transition. Finally, preliminary results of time-resolved pump-probe spectroscopy confirm that the CT exciton or one of its constituent parts couples strongly to phonons, and we ...
Date: February 27, 2001
Creator: Schumacher, Andreas B.
Partner: UNT Libraries Government Documents Department

Nuclear magnetic resonance: Its role as a microscopic probe of the electronic and magnetic properties of High-{Tc} superconductors and related materials

Description: NMR experiments are reported for Sr{sub 2}CuO{sub 2}Cl{sub 2}, HgBa{sub 2}CuO{sub 4+d}, YNi{sub 2}B{sub 2}C and YBa{sub 2}Cu{sub 3}O{sub 7}. NMR studies typify three different aspects of microscopic properties of HTSC. In non-superconducting antiferromagnetic (AF) prototype Sr{sub 2}CuO{sub 2}Cl{sub 2}, we used NMR to investigate Cu{sup 2+} correlated spin dynamics and AF phase transition in CuO2 layers. In the superconductors, we used NMR both to investigate the electronic properties of the Fermi-liquid in normal and superconducting states and to investigate flux lattice and flux-line dynamics in the superconducting state in presence of magnetic field. A summary of each study is given: {sup 35}Cl NMR was measured in Sr{sub 2}CuO{sub 2}Cl{sub 2} single crystals with T{sub N}=257K. {sub 35}Cl NMR relaxation rates showed crossover of Cu{sup 2+} spin dynamics from Heisenberg to XY-like correlation at 290 K well above T{sub N}. A field-dependent T{sub N} for H{perpendicular}c was observed and explained by a field-induced Ising-like anisotropy in ab plane. {sup 199}Hg NMR was measured in HgBa{sub 2}CuO{sub 4+d}. Properties of the Fermi-liquid are characterized by a single-spin fluid picture and opening of a spin pseudo-gap at q=0 above {Tc}. Below {Tc}, spin component of Knight shift decreases rapidly in agreement with prediction for d-wave pairing scheme. {sup 11}B and {sup 89}Y NMR/magnetization were measured in YNi{sub 2}B{sub 2}C. Temperature dependence of {sup 11}B Knight shift and of the NSLR gave a normal state which agrees with the Korringa relation, indicating that the AF fluctuations on the Ni sublattice are negligible. Opening of the superconducting gap obeys BCS. A NMR approach to investigate vortex thermal motion in HTSC is presented, based on contribution of thermal flux-lines motion to both T{sub 2}{sup {minus}1} and T{sub 1}{sup {minus}1}. Effects are demonstrated in YBa{sub 2}Cu{sub 3}O{sub 7} and HgBa{sub 2}CuO{sub 4+d}.
Date: December 27, 1995
Creator: Suh, Byoung Jin
Partner: UNT Libraries Government Documents Department

Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

Description: Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO{sub 2} films] revealed that MnO{sub 2} film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO{sub 2} films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO{sub 2} films showed that the Fe(III)-doped RuO{sub 2}-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO{sub 2} films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H{sub 2}O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb{sub 10}Sn{sub 20}Ti{sub 70}, Cu{sub 63}Ni{sub 37} and Cu{sub 25}Ni{sub 75} alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu{sub 63}Ni{sub 37} alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO{sub 3}{sup -} at the Cu-Ni alloy electrode is superior to the response at the pure Cu and Ni electrodes. This is explained on the basis of the synergism of the two different metal sites at these binary ...
Date: August 27, 2002
Creator: Simpson, Brett Kimball
Partner: UNT Libraries Government Documents Department

Molecular Design of Branched and Binary Molecules at Ordered Interfaces

Description: This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.
Date: December 27, 2005
Creator: Genson, Kirsten Larson
Partner: UNT Libraries Government Documents Department

The Theory of Random Laser Systems

Description: Studies of random laser systems are a new direction with promising potential applications and theoretical interest. The research is based on the theories of localization and laser physics. So far, the research shows that there are random lasing modes inside the systems which is quite different from the common laser systems. From the properties of the random lasing modes, they can understand the phenomena observed in the experiments, such as multi-peak and anisotropic spectrum, lasing mode number saturation, mode competition and dynamic processes, etc. To summarize, this dissertation has contributed the following in the study of random laser systems: (1) by comparing the Lamb theory with the Letokhov theory, the general formulas of the threshold length or gain of random laser systems were obtained; (2) they pointed out the vital weakness of previous time-independent methods in random laser research; (3) a new model which includes the FDTD method and the semi-classical laser theory. The solutions of this model provided an explanation of the experimental results of multi-peak and anisotropic emission spectra, predicted the saturation of lasing modes number and the length of localized lasing modes; (4) theoretical (Lamb theory) and numerical (FDTD and transfer-matrix calculation) studies of the origin of localized lasing modes in the random laser systems; and (5) proposal of using random lasing modes as a new path to study wave localization in random systems and prediction of the lasing threshold discontinuity at mobility edge.
Date: June 27, 2002
Creator: Jiang, Xunya
Partner: UNT Libraries Government Documents Department

Numerical Simulation of the Performance Characteristics, Instability, and Effects of Band Gap Grading in Cadmium Telluride Based Photovoltaic Devices

Description: Using computer simulations, the performance of several CdTe based photovoltaic structures has been studied. The advantages and disadvantages of band gap grading, through the use of (Zn, Cd)Te, have also been investigated in these structures. Grading at the front interface between a CdS window layer and a CdTe absorber layer, can arise due to interdiffusion between the materials during growth or due to the intentional variation of the material composition. This grading has been shown to improve certain performance metrics, such as the open-circuit voltage, while degrading others, such as the fill factor, depending on the amount and distance of the grading. The presence of a Schottky barrier as the back contact has also been shown to degrade the photovoltaic performance of the device, resulting in a characteristic IV curve. However, with the appropriate band gap grading at the back interface, it has been shown that the performance can be enhanced through more efficient carrier collection. These results were then correlated with experimental observations of the performance degradation in devices subjected to light and heat stress.
Date: June 27, 2001
Creator: Petersen, Michael David
Partner: UNT Libraries Government Documents Department