Physical Sciences and Mathematics Commons^™

Syntheses, Photophysics, & Application Of Porphyrinic Metal-Organic Frameworks, Zachary L. Magnuson

USF Tampa Graduate Theses and Dissertations

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface …

Syntheses, Photophysics, & Application Of Porphyrinic Metal-Organic Frameworks, Zachary L. Magnuson

USF Tampa Graduate Theses and Dissertations

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface …

Development And Characterization Of Lead & Lead-Free Perovskite Solar Cell Materials, Rubaiya Murshed

UNLV Theses, Dissertations, Professional Papers, and Capstones

In recent years, perovskite photovoltaic technology has offered enormous viability and dimensionality in solar cell research. As a light-harvesting active layer, Perovskite generated remarkable development in device efficiency of 25.7% for the single-junction solar cell, and over 33% for the perovskite/silicon tandem solar cell. Also, perovskite-perovskite tandem solar cell (also called all-perovskite tandem solar cell) shows great potential in device performance and achieved a power conversion efficiency (PCE) of 26.4%. Transitioning photovoltaic technology from the laboratory to commercial products, high PCE, low cost, long lifetime, and low toxicity are some of the critical factors to consider during material selection. Pb-halide …

Fabrication, Measurements, And Modeling Of Semiconductor Radiation Detectors For Imaging And Detector Response Functions, Corey David Ahl

Doctoral Dissertations

In the first part of this dissertation, we cover the development of a diamond semiconductor alpha-tagging sensor for associated particle imaging to solve challenges with currently employed scintillators. The alpha-tagging sensor is a double-sided strip detector made from polycrystalline CVD diamond. The performance goals of the alpha-tagging sensor are 700-picosecond timing resolution and 0.5 mm spatial resolution. A literature review summarizes the methodology, goals, and challenges in associated particle imaging. The history and current state of alpha-tagging sensors, followed by the properties of diamond semiconductors are discussed to close the literature review. The materials and methods used to calibrate the …

Total Absorption Spectroscopy Of Mo-106 And Tc-106, Michael Cooper

Doctoral Dissertations

Total absorption spectroscopy is a method of gamma-ray spectroscopy that has gained prominence in the past several decades, as nuclear data revisions are performed on older nuclear data, which is often incomplete. A strong understanding of underlying nuclear data, particularly fission and beta decay data, is essential for nuclear reactors and nuclear fuel decay heat. This PhD work involves the analysis of fission fragments 106Mo [Mo-106] and 106Tc [Tc-106]. These neutron rich isotopes contribute upwards of 6% of the cumulative fission yield of 241Pu [Pu-241] fission, and 4% of 239Pu [Pu-239] fission. Prior data for these two fission fragments only …

Spectroscopic Studies On Silicon And Chalcopyrite Materials For Solar Energy Applications, Amandee Hua

UNLV Theses, Dissertations, Professional Papers, and Capstones

In this dissertation, silicon-based materials for photovoltaics and chalcopyrite-based materials for photoelectrochemical water splitting are investigated using various spectroscopic and microscopic techniques. Although silicon dominates the photovoltaic market, further improvement can be made by using an alternative low temperature passivation approach. Currently, thermally grown SiO2 passivation is commonly used for silicon solar cells. However, this technique requires high processing temperatures (>800 °C), which increases the thermal budget, potentially decreases the bulk quality of Si, and can lead to difficulties in implementing in production lines. Here, a S-based passivation approach is studied that require lower processing temperatures of ~550 °C. …

Ultrasensitive Tapered Optical Fiber Refractive Index, Erem Ujah, Meimei Lai, Gymama Slaughter

Electrical & Computer Engineering Faculty Publications

Refractive index (RI) sensors are of great interest for label-free optical biosensing. A tapered optical fiber (TOF) RI sensor with micron-sized waist diameters can dramatically enhance sensor sensitivity by reducing the mode volume over a long distance. Here, a simple and fast method is used to fabricate highly sensitive refractive index sensors based on localized surface plasmon resonance (LSPR). Two TOFs (l = 5 mm) with waist diameters of 5 µm and 12 µm demonstrated sensitivity enhancement at λ = 1559 nm for glucose sensing (5-45 wt%) at room temperature. The optical power transmission decreased with increasing glucose concentration due …

Nondestructive Evaluation Of 3d Printed, Extruded, And Natural Polymer Structures Using Terahertz Spectroscopy And Imaging, Alexander T. Clark

Dissertations

Terahertz (THz) spectroscopy and imaging are considered for the nondestructive evaluation (NDE) of various three-dimensional (3D) printed, extruded, and natural polymer structures. THz radiation is the prime candidate for many NDE challenges due to the added benefits of safety, increased contrast and depth resolution, and optical characteristic visualization when compared to other techniques. THz imaging, using a wide bandwidth pulse-based system, can evaluate the external and internal structure of most nonconductive and nonpolar materials without any permanent effects. NDE images can be created based on THz pulse attributes or a material’s spectroscopic characteristics such as refractive index, attenuation coefficient, or …

Enigma - Ongoing Development Towards Novel Beta-Decay Spectroscopy Station At Isolde, Philipp Wagenknecht

Masters Theses

Beta decay and collinear laser spectroscopy are proven efficient tools to study nuclear structure far from stability. Two areas of significance are investigations into nuclear deformation and shape coexistence, as well as delayed neutron emissions used in nuclear energy applications. This contribution presents the ongoing development towards a novel beta-decay spectroscopy station for the VITO experiment at CERN’s radioactive ion beam facility ISOLDE. The setup will utilize both collinear laser spectroscopy and beta-decay spectroscopy to measure the energy and spin-parities of the ground and excited states of radioactive beams. Initial designs of the support structure, magnetic field, and detector array …

Towards Plasmon Mapping Of Sers-Active Ag Dewetted Nanostructures Using Spels, Mohamed Beshr, E. Dexter, Paul E. Tierney, Aidan Meade, Shane Murphy, George Amarandei

Articles

Thermal dewetting of silver thin flm can lead to SERS-active Ag nanoparticles. Here, we report our progress towards using scanning probe energy loss spectroscopy (SPELS) to map the plasmonic behaviour of SERS-active Ag nanoparticles (NP) by investigating NPs produced through the dewetting study of Ag thin flms on SiO2/Si and Ti/SiO2/Si substrates. The nanoparticles size and spatial distribution were controlled by the deposition and thermal annealing parameters. The results of preliminary SPELS measurements of these structures, alongside SERS data show that there is a correlation between the Raman enhancement and the nanoparticle size and interparticle spacing.

Ultrafast Spectroscopy Of Air Lasing In Filaments, Brian Robert Kamer

Optical Science and Engineering ETDs

Filamentation in air is a phenomenon that has been extensively investigated for the last two decades. At sufficiently high intensity, even air is a nonlinear medium. These intensities are reached with ultrashort pulses (50 to 100 fs) of more than 1 J energy, which self-focus in air, reach ionizing intensities of oxygen and nitrogen, creating a plasma that defocuses the beam. The air filament is a self-induced waveguide resulting from a balance of focusing and defocusing. In this work new techniques were developed to visualize and analyze this phenomenon through its emission, in particu- lar the UV emission of the …

The Profound Photophysical Effects Of Organic Chromophore Connectivity And Coupling, David J. Walwark Jr

Nanoscience and Microsystems ETDs

Through-bond and through-space interactions between chromophores are shown to have wide-ranging effects on photophysical outcomes upon light absorption in organic molecules. In collapsed poly(3-hexylthiophene), through-space coupling creates hybrid chromophores that act as energy sinks for nearby excitons and favorable sites for molecular oxygen to dock. Upon excitation with visible light the highly-coupled chromophores react with the docked oxygen and subsequently do not quench nearby excitons as efficiently. In tetramer arrays of perylene diimide chromophores the central moiety through-bond connectivity is synthesized in two variants which exhibit vastly different single-molecule blinking behavior and theoretically-predicted electronic transition character. In the more-connected tetramer …

3d-Printable And Open-Source Modular Smartphone Visible Spectrophotometer, Brandon Winters, Nick Banfield, Cassandra Dixon, Anna Swensen, Dakota Holman, Braxton Fillbrown

Chemistry Faculty Publications

The past four decades have brought significant and increasingly rapid changes to the world of instrument design, fabrication, and availability due to the emergence of 3D printing, open-source code and equipment, and low-cost electronics. These, along with other technological advances represent a nexus in time ripe for the wide-spread production and availability of low-cost sophisticated scientific equipment. To that end, the design of a 3D printable and open-source, modular spectrometer is described. This specific instrument is distinctly different from others that have been reported in recent years in that it was designed outside of the “black box” paradigm of …

Neutron Energy Tuning Assemblies For Nuclear Weapon Environment Applications At The National Ignition Facility, Nicholas J. Quartemont

Theses and Dissertations

An energy tuning assembly was developed to spectrally shape the National Ignition Facility deuterium-tritium fusion neutron source to a notional thermonuclear and prompt fission neutron spectrum to fulfill neutron source capability gaps. The experimental neutron environment was characterized with activation dosimetry, neutronics and covariance models, and unfolded to determine the as-fielded neutron spectrum. The first energy tuning assembly was demonstrated to create synthetic spectrally accurate post-detonation fission products, enhancing U.S. technical nuclear forensics capabilities. ATHENA, a second-generation energy tuning assembly, was also optimized to meet similar objectives, but the new platform neutron fluence efficiency was increased by a factor of …

High Frequency Electron Spin Resonance Investigations On Quasi-Two-Dimensional Chromium Halide Magnets, Christian Saiz

Open Access Theses & Dissertations

Broadening the knowledge and understanding on the magnetic correlations in van der Waals layered magnets is critical in realizing their potential next-generation applications in devices such as spintronics. In this study, we employ high frequency (ν = 120 GHz, 240 GHz) electron spin resonance (ESR) spectroscopy on plate-like CrX3 (where X = Cl, Br, I) to gain insight into the magnetic interactions as a function of temperature (200 – 4.4 K) and the angle of rotation θ (degrees). We find that the temperature dependence of the ESR linewidth is well described by the Ginzburg-Landau critical model, indicative of antiferromagnetic correlations …

Synthesis Of Graphene Using Plasma Etching And Atmospheric Pressure Annealing: Process And Sensor Development, Andrew Robert Graves

Graduate Theses, Dissertations, and Problem Reports

Having been theorized in 1947, it was not until 2004 that graphene was first isolated. In the years since its isolation, graphene has been the subject of intense, world-wide study due to its incredibly diverse array of useful properties. Even though many billions of dollars have been spent on its development, graphene has yet to break out of the laboratory and penetrate mainstream industrial applications markets. This is because graphene faces a ‘grand challenge.’ Simply put, there is currently no method of manufacturing high-quality graphene on the industrial scale. This grand challenge looms particularly large for electronic applications where the …

Organic/Inorganic Interfacial Interactions Affecting Metal Reactivity: Water Treatment And Sensor Applications, Mohamed Nabil Shaikh

Civil Engineering ETDs

The aim of this dissertation was to investigate the interactions occurring at the organic – inorganic interface between solid media and aqueous contaminants for water treatment and sensor applications. The gaps in current literature on these interfacial organic-inorganic interactions must be bridged in order to develop advanced water treatment and monitoring technologies for improving water quality and thus, restore and protect the contaminated water resources. As a part of this dissertation, manganese oxides-based composites and electrospun polymer mats were developed and investigated for gaining mechanistic insights of organic (bisphenol A and acetaminophen) and inorganic (uranium) contaminants removal, respectively. These reactions …

Light Scattering In Diffraction Limit Infrared Imaging, Ghazal Azarfar

Theses and Dissertations

Fourier Transform Infrared (FTIR) microspectroscopy is a noninvasive technique for chemical imaging of micrometer size samples. Employing an infrared microscope, an infrared source and FTIR spectrometer coupled to a microscope with an array of detectors (128 x 128 detectors), enables collecting combined spectral and spatial information simultaneously. Wavelength dependent images are collected, that reveal biochemical signatures of disease pathology and cell cycle. Single cell biochemistry can be evaluated with this technique, since the wavelength of light is comparable to the size of the objects of interest, which leads to additional spectral and spatial effects disturb biological signatures and can confound …

Development Of A Ground-Based Aerial-Tracking Instrument For Open-Path Spectroscopy To Monitor Atmospheric Constituents, Haden Hodges

Civil Engineering Undergraduate Honors Theses

A ground-based aerial-tracking instrument, known as the Ground Tracker, designed to provide spectral data to quantify greenhouse gases is under development. The Ground Tracker includes an Optical System including a high power rifle scope, video camera, and spectrometer used to locate an active light source from the Emitter, and collect spectral data by utilizing an actuating mirror. The implementation of this instrument could be made low cost by utilizing existing weather balloon infrastructure to allow the Emitter to be placed into the lower stratosphere. The recovery of the emitter will be possible by tracking the GPS coordinates. Weather balloon instrument …

3d Printable Optomechanical Cage System With Enclosure, Brandon Winters, David Shepler

Chemistry Faculty Publications

The advent of the computer-age in the mid to late 20th century brought the development of sophisticated scientific equipment for myriad chemical analyses. The field of spectroscopy alone has seen significant advances in data collection, processing, and analysis due principally to the incorporation of microprocessors. While it is clear computers have revolutionized the field of instrumental chemical analysis their impact is pervasive through every segment of our lives. From word processing, data management, and Computer Aided Design in our work environments to social media, crowd funding, and digital news at home, technology is everywhere. This work seeks to incorporate the …

Multispectral Identification Array, Zachary D. Eagan

Computer Engineering

The Multispectral Identification Array is a device for taking full image spectroscopy data via the illumination of a subject with sixty-four unique spectra. The array combines images under the illumination spectra to produce an approximate reflectance graph for every pixel in a scene. Acquisition of an entire spectrum allows the array to differentiate objects based on surface material. Spectral graphs produced are highly approximate and should not be used to determine material properties, however the output is sufficiently consistent to allow differentiation and identification of previously sampled subjects. While not sufficiently advanced for use as a replacement to spectroscopy the …

Label-Free Raman Imaging To Monitor Breast Tumor Signatures, John Ciubuc

Open Access Theses & Dissertations

Methods built on Raman spectroscopy have shown major potential in describing and discriminating between malignant and benign specimens. Accurate, real-time medical diagnosis benefits in substantial improvements through this vibrational optical method. Not only is acquisition of data possible in milliseconds and analysis in minutes, Raman allows concurrent detection and monitoring of all biological components. Besides validating a significant Raman signature distinction between non-tumorigenic (MCF-10A) and tumorigenic (MCF-7) breast epithelial cells, this study reveals a label-free method to assess overexpression of epidermal growth factor receptors (EGFR) in tumor cells. EGFR overexpression sires Raman features associated with phosphorylated threonine and serine, and …

A Method For Reflectance Index Wavelength Selection From Moisture-Controlled Soil And Crop Residue Samples, Ali Hamidisepehr, Michael P. Sama, Aaron P. Turner, Ole O. Wendroth

Biosystems and Agricultural Engineering Faculty Publications

Reflectance indices are a method for reducing the dimensionality of spectral measurements used to quantify material properties. Choosing the optimal wavelengths for developing an index based on a given material and property of interest is made difficult by the large number of wavelengths typically available to choose from and the lack of homogeneity when remotely sensing agricultural materials. This study aimed to determine the feasibility of using a low-cost method for sensing the moisture content of background materials in traditional crop remote sensing. Moisture-controlled soil and wheat stalk residue samples were measured at varying heights using a reflectance probe connected …

Searching To Distinguish Defects And The Presence Of Negative Capacitance, Thaddeus Cox

Senior Theses

In the search for solar cells with lower manufacturing costs, thin film technology was developed. These thin films are only micrometers thick and are grown at relatively low temperatures, resulting in films with imperfections known as defects. Defects can cause thin film solar cells to have lower efficiencies than their single crystalline counterparts. In order to create more efficient thin film solar cells the physical mechanisms behind defects need to be investigated by sensitive techniques. Capacitance measurements of solar cells detect minute changes in charge in the material. For that reason, capacitance is used to electrically characterize the solar cell. …

Excitonic States In Crystalline Organic Semiconductors: A Condensed Matter Approach, Lane Wright Manning

Graduate College Dissertations and Theses

In this work, a new condensed matter approach to the study of excitons based on crystalline thin films of the organic molecule phthalocyanine is introduced. The premise is inspired by a wealth of studies in inorganic semiconductor ternary alloys (such as AlGaN, InGaN, SiGe) where tuning compositional disorder can result in exciton localization by alloy potential fluctuations. Comprehensive absorption, luminescence, linear dichroism and electron radiative lifetime studies were performed on both pure and alloy samples of metal-free octabutoxy-phthalocyanine and transition metal octabutoxy-phthalocyanines, where the metal is Mn, Co, Ni, and Cu. Varying the ratios of the metal to metal-free phthalocyanines …

Improved Terahertz Modulation Using Germanium Telluride (Gete) Chalcogenide Thin Films, Alexander H. Gwin, Christopher H. Kodama, Tod V. Laurvick, Ronald Coutu Jr., Philip F. Taday

Faculty Publications

We demonstrate improved terahertz (THz) modulation using thermally crystallized germanium telluride (GeTe) thin films. GeTe is a chalcogenide material that exhibits a nonvolatile, amorphous to crystalline phase change at approximately 200 °C, as well as six orders of magnitude decreased electrical resistivity. In this study, amorphous GeTe thin films were sputtered on sapphire substrates and then tested using THz time-domain spectroscopy (THz-TDS). The test samples, heated in-situ while collecting THz-TDS measurements, exhibited a gradual absorbance increase, an abrupt nonvolatile reduction at the transition temperature, followed by another gradual increase in absorbance. The transition temperature was verified by conducting similar thermal …

Coupling Nuclear Induced Phonon Propagation With Conversion Electron Mössbauer Spectroscopy, Michael J. Parker

Theses and Dissertations

Mössbauer spectroscopy is a very sensitive measurement technique (10^-8 eV) which prompted motivation for the experiment described in this thesis. Namely, can a sensitive detection system be developed to detect nuclear recoils on the order of 10 to 100 of eVs? The hypothesis that this thesis tests is: Nuclear induced phonon bursts caused by Rutherford scattered alphas, decayed from ²⁴¹Am, in a type-310 stainless steel material can couple with 7.3 keV conversion electron Mössbauer events at the other end of the material which will have a statistically significant effect on a Mössbauer spectrum. The phonon bursts produced by …

Pulsed Inductive Plasma Studies By Spectroscopy And Internal Probe Methods, Warner C. Meeks

Doctoral Dissertations

The broad effort of the Missouri Plasmoid Experiment is to elucidate the energy conversion processes in a pulsed inductive discharge due to the presence of plasma. The test article is a 440 to 490 kHz theta-pinch (or solenoidal) geometry coil with a stored energy of around 80 joules. In this work experimental hydrogen, helium, argon and xenon data at back-fill pressures of 10 to 100 mTorr (1.3 to 133.3 Pa) are obtained and interpreted. Spectral and internal probe studies were performed on MPX Mk.I and Mk.II devices, respectively. IR spectra were acquired in the Mk.I device for argon and xenon. …

Spectroscopic Investigation Of The Chemical And Electronic Properties Of Chalcogenide Materials For Thin-Film Optoelectronic Devices, Kimberly Horsley

UNLV Theses, Dissertations, Professional Papers, and Capstones

Chalcogen-based materials are at the forefront of technologies for sustainable energy production. This progress has come only from decades of research, and further investigation is needed to continue improvement of these materials.

For this dissertation, a number of chalcogenide systems were studied, which have applications in optoelectronic devices, such as LEDs and Photovoltaics. The systems studied include Cu(In,Ga)Se2 (CIGSe) and CuInSe2 (CISe) thin-film absorbers, CdTe-based photovoltaic structures, and CdTe-ZnO nanocomposite materials. For each project, a sample set was prepared through collaboration with outside institutions, and a suite of spectroscopy techniques was employed to answer specific questions about the system. These …

Optimization Of Plasmon Decay Through Scattering And Hot Electron Transfer, Drew Dejarnette

Graduate Theses and Dissertations

Light incident on metal nanoparticles induce localized surface oscillations of conductive electrons, called plasmons, which is a means to control and manipulate light. Excited plasmons decay as either thermal energy as absorbed phonons or electromagnetic energy as scattered photons. An additional decay pathway for plasmons can exist for gold nanoparticles situated on graphene. Excited plasmons can decay directly to the graphene as through hot electron transfer. This dissertation begins by computational analysis of plasmon resonance energy and bandwidth as a function of particle size, shape, and dielectric environment in addition to diffractive coupled in lattices creating a Fano resonance. With …