Materials Chemistry Commons^™

Photovoltages In Polycrystalline Mosaic Solar Cells, Steluta A. Dinca, Eric A. Schiff

Chemistry - All Scholarship

In some thin-film solar cells the light-absorbing layer is a mosaic of crystalline grains whose boundaries run from the back to the front of the cell. We used the semiconductor modeling software Sesame to do numerical calculations of the optoelectronic properties of such cells assuming that recombination of minority photocarriers occurs primarily at the grain boundaries. The work complements analytical results for diffusion-limited recombination at grain boundaries and dislocations. We chose idealized n-CdS/p-CdTe solar cells for illustration. We find that the open-circuit voltage, V_oc, under illumination declines logarithmically with increasing ratio D/θ², where D is the …

Data-Driven Approaches To Complex Materials: Applications To Amorphous Solids, Dil Kumar Limbu

Dissertations

While conventional approaches to materials modeling made significant contributions and advanced our understanding of materials properties in the past decades, these approaches often cannot be applied to disordered materials (e.g., glasses) for which accurate total-energy functionals or forces are either not available or it is infeasible to employ due to computational complexities associated with modeling disordered solids in the absence of translational symmetry. In this dissertation, a number of information-driven probabilistic methods were developed for the structural determination of a range of materials including disordered solids to transition metal clusters. The ground-state structures of transition-metal clusters of iron, nickel, and …

Interactions Of Organic Fluorophores With Plasmonic Surface Lattice Resonances, Robert J. Collison

Dissertations, Theses, and Capstone Projects

It is common knowledge that metals, alloys and pure elements alike, are lustrous and reflective, the more so when a metal surface is flat, polished, and free from oxidation and surface fouling. However, some metals reflect visible light, in the 380 nm to 740 nm range of wavelengths, much more strongly than others. In particular, some metals reflect wavelengths in certain portions of the ultraviolet (UV), visible, and near-infrared (NIR) regime, let us say 200 nm to 2000 nm, while absorbing light strongly in other segments of this range. There are several factors that account for this difference between various …

Nanoengineered Materials For Energy Conversion & Storage Applications: A Density Functional Theory Study, Ahmed Biby

Theses and Dissertations

The conventional approach for the development of novel materials has become long relative to the desired product development cycle. Thus, the sluggish pace of the development of materials within the conventional approach hinders the rapid transformation of the scientific outcomes into useful technological products. To this end, the field of hierarchical materials informatics evolved to bridge this gap. In this field, the multiscale material internal structure is considered the starting point and the core of this approach. This being said, the density functional theory (DFT) was used to generate useful materials data for the advancement of the hierarchical materials data-bases …

Numerical Reconstruction Of Spalled Particle Trajectories In An Arc-Jet Environment, Raghava S. C. Davuluri, Sean C. C. Bailey, Kaveh A. Tagavi, Alexandre Martin

Mechanical Engineering Faculty Publications

To evaluate the effects of spallation on ablative material, it is necessary to evaluate the mass loss. To do so, a Lagrangian particle trajectory code is used to reconstruct trajectories that match the experimental data for all kinematic parameters. The results from spallation experiments conducted at the NASA HYMETS facility over a wedge sample were used. A data-driven adaptive methodology was used to adapts the ejection parameters until the numerical trajectory matches the experimental data. The preliminary reconstruction results show that the size of the particles seemed to be correlated with the location of the ejection event. The size of …

Fabrication Of Metal-Silicon Nanostructures By Reactive Laser Ablation In Liquid, Eric J. Broadhead

Theses and Dissertations

Metal-silicon nanostructures are a growing area of research due to their applications in multiple fields such as biosensing and catalysis. In addition, silicon can provide strong support effects to metal nanoparticles while being more cost effective than traditionally used supports, like titania. Traditional wet-chemical methods are capable of synthesizing metal-silicon nanostructures with a variety of composition and nanoparticle shapes, but they often require high temperatures, toxic solvents, strong reducing agents, or need capping agents added to stabilize the nanoparticles. Laser processing is an emerging technique capable of synthesizing metal-silicon composite surfaces that offers a faster, simpler, and greener synthesis route …

Predicting Material Properties: Applications Of Multi-Scale Multiphysics Numerical Modeling To Transport Problems In Biochemical Systems And Chemical Process Engineering, Tom Pace

Theses and Dissertations--Physics and Astronomy

Material properties are used in a wide variety of theoretical models of material behavior. Descriptive properties quantify the nature, structure, or composition of the material. Behavioral properties quantify the response of the material to an imposed condition. The central question of this work concerns the prediction of behavioral properties from previously determined descriptive properties through hierarchical multi-scale, multiphysics models implemented as numerical simulations. Applications covered focus on mass transport models, including sequential enzyme-catalyzed reactions in systems biology, and an industrial chemical process in a common reaction medium.

Development Of Synthetic Coal Char Simulant For Microwave Conversion Studies: A Computationally-Driven Approach, Kevin A. Hager

Graduate Theses, Dissertations, and Problem Reports

Recent experimental demonstration of new reaction windows for coal char/methane reactions that are less energy-intensive, provides innovation for modular reactors. However, the correlation of the exact mechanism for the enhancement of these reaction windows is not certain. This study investigates the simplification of these experimental studies by developing a well-characterized coal char simulant. The approach involves using a computational approach to screen macroscopic composition to replicate the dielectric and compositional response of actual char. This study is focused on PRB coal char. A discrete element method (DEM) technique was used to simulate the packing of coal chars to give the …

Ligand Effects On Electronic, Magnetic, And Catalytic Properties Of Clusters And Cluster Assemblies, Dinesh Bista 9288522

Theses and Dissertations

Ligands commonly protect metallic clusters against reacting with outside reactants. However, ligands can also be used to control the redox properties enabling the formation of super donors/acceptors that can donate/accept multiple electrons. This thesis focuses on how the ligands can be used to control the electronic and magnetic features of clusters and ligand stabilized cluster-based assemblies, leading to nano pn junctions with directed transport, the possibility of light-harvesting, and catalysts for cross-coupling reactions. The thesis addresses three distinct classes of clusters and their applications. The first class of cluster “metal chalcogen clusters” is the central idea of the thesis focused …

Treated Hfo2 Based Rram Devices With Ru, Tan, Tin As Top Electrode For In-Memory Computing Hardware, Yuvraj Dineshkumar Patel

Theses

The scalability and power efficiency of the conventional CMOS technology is steadily coming to a halt due to increasing problems and challenges in fabrication technology. Many non-volatile memory devices have emerged recently to meet the scaling challenges. Memory devices such as RRAMs or ReRAM (Resistive Random-Access Memory) have proved to be a promising candidate for analog in memory computing applications related to inference and learning in artificial intelligence. A RRAM cell has a MIM (Metal insulator metal) structure that exhibits reversible resistive switching on application of positive or negative voltage. But detailed studies on the power consumption, repeatability and retention …

Local Structure And Dynamic Studies Of Mixed Ch4-Co2 Gas Hydrates Via Computational Simulation And Neutron Scattering, Bernadette Rita Cladek

Doctoral Dissertations

Permeated throughout the ocean floor and arctic permafrost, natural gas hydrates contain an estimated 3000 trillion cubic meters, over three times that of traditional shale deposits, of CH₄ that is accessible for extraction. Gas hydrates are a crystal structure in which water molecules form a cage network, the host, through hydrogen bonds while trapping a guest molecule such as CH₄ in the cavities. These compounds form naturally where the appropriate low temperature and high pressure conditions occur. A promising and tested method of methane recovery is through exchange with CO₂, which energetically takes place of the …

3-D Fabry–Pérot Cavities Sculpted On Fiber Tips Using A Multiphoton Polymerization Process, Jonathan W. Smith, Jeremiah C. Williams, Joseph S. Suelzer, Nicholas G. Usechak, Hengky Chandrahalim

Faculty Publications

This paper presents 3-D Fabry–Pérot (FP) cavities fabricated directly onto cleaved ends of low-loss optical fibers by a two-photon polymerization (2PP) process. This fabrication technique is quick, simple, and inexpensive compared to planar microfabrication processes, which enables rapid prototyping and the ability to adapt to new requirements. These devices also utilize true 3-D design freedom, facilitating the realization of microscale optical elements with challenging geometries. Three different device types were fabricated and evaluated: an unreleased single-cavity device, a released dual-cavity device, and a released hemispherical mirror dual-cavity device. Each iteration improved the quality of the FP cavity's reflection spectrum. The …

Adsorption And Reconfiguration Of Amphiphiles At Silica-Water Interfaces: Role Of Electrostatic Interactions, Van Der Waals Forces And Hydrogen Bonds, Yao Wu

LSU Doctoral Dissertations

The ability to explore and predict metastable structures of hybrid self-assemblies is of central importance for the next generation of advanced materials with novel properties. As compared to their thermodynamically stable forms, the kinetically stabilized materials show improved functionality potentially over their stable counterparts. The self-assembly processes usually originate from weak intermolecular interactions, involving a dynamic competition between attractive and repulsive interactions. These weak forces, including van der Waals (vdW), electrostatic interaction and the hydrogen bonding (H-bonding), can be tuned by external stimuli, e.g., confinement, temperature and ionization, and consequently driving hybrid materials into different configurations. It is challenging to …

Organic-Inorganic Halide Perovskite Nanocrystals And Solar Cells, Rui Guo

FIU Electronic Theses and Dissertations

A great challenge facing humanity in the 21^st century is finding inexhaustible and inexpensive energy sources to power the planet. Renewable energies are the best solutions because of their abundance, diversity, and pollution-free emission. Solar energy is the cleanest and most abundant renewable energy source available. In the continuing quest for efficient and low-cost solar cells, perovskite solar cells (PSCs) have emerged as a potential replacement for silicon solar cells. Since 2009, the record efficiencies of PSCs have been skyrocketing from 3.8 % to 25.2 % and are now approaching the theoretical limit. Along with the three-dimensional perovskites used …

Pressure Driven Desalination Utilizing Nanomaterials, Fangyou Xie

Master's Theses

Nanomaterials such as graphene oxide and carbon nanotubes, have demonstrated excellent properties for membrane desalination, including decrease of maintenance, increase of flux rate, simple solution casting, and impressive chemical inertness. Here, two projects are studied to investigate nanocarbon based membrane desalination. The first project is to prepare hybrid membranes with amyloid fibrils intercalated with graphene oxide sheets. The addition of protein amyloid fibrils expands the interlayer spacing between graphene oxide nanosheets and introduces additional functional groups in the diffusion pathways, resulting in increase of flux rate and rejection rate for the organic dyes. Amyloid fibrils also provide structural assistance to …

Electronic And Local Structures Of Pt-Based Bimetallic Alloy And Core-Shell Systems, Jiatang Chen

Electronic Thesis and Dissertation Repository

This thesis investigates the electronic structure of Pt for catalysis applications. The importance of the Pt 5d band is discussed in terms of the bonding capability of Pt. The oxygen reduction reaction in proton exchange membrane fuel cells is chosen as the catalytic reaction model to illustrate the effect of Pt 5d states on Pt-O interaction. Pt-based bimetallic systems are introduced as a solution for the high price and limited resources of Pt. Despite lower usage of Pt, the tuning capability to optimize the Pt 5d band in bimetallic catalysts is supposed to provide superior catalytic activity. Advanced synchrotron X-ray …

Embedded Gold Nanoparticles For Metal Enhanced Photoluminescence, Hasna Alali

Dissertations

Noble metal nanoparticles (MNPs) have attracted great attention in electronics, solar cells and catalysis. Their unique optical properties and biocompatibility makes them useful in biological applications like imaging, drug delivery, therapy and diagnostic. At the surface of MNPs the collective oscillation of free electrons resonates with a particular wavelength of incident light, generating the Localized Surface Plasmons Resonance (LSPR). LSPR results in absorption and scattering of incident light. Scattering results in reflecting photons and absorption leads to enhanced photoluminescence and quenching of fluorophores, if the fluorophore is in the vicinity of MNPs.

Most of the studies in this regard have …

Investigation Of The Structural, Electronic, And Thermoelectric Properties Of Mono- Chalcogenides, Aida Sheibani

Graduate Theses and Dissertations

The structural, electronic, and thermoelectric properties of GeTe are studied using density functional theory and Boltzmann transport equations. This material has a rhombohedral crystal structure in ambient temperature with a ferroelectric behavior due to lack of inversion symmetry. This study suggests that the presence of asymmetry in GeTe can lead to an improvement in the thermoelectric properties of this material. In addition, studies on introducing Group III, IV, and V dopants to GeSe show that while these impurities can improve the power factor and decrease the lattice thermal conductivity, they cannot enhance the figure of merit.

Nanoscale Colocalization Of Fluorogenic Probes Reveals The Role Of Oxygen Vacancies In The Photocatalytic Activity Of Tungsten Oxide Nanowires, Meikun Shen, Tianben Ding, Steven T. Hartman, Fudong Wang, Christina Krucylak, Zheyu Wang, Che Tan, Bo Yin, Rohan Mishra, Matthew D. Lew, Bryce Sadtler

Electrical & Systems Engineering Publications and Presentations

Defect engineering is a strategy that has been widely used to design active semiconductor photocatalysts. However, understanding the role of defects, such as oxygen vacancies, in controlling photocatalytic activity remains a challenge. Here, we report the use of chemically triggered fluorogenic probes to study the spatial distribution of active regions in individual tungsten oxide nanowires using super-resolution fluorescence microscopy. The nanowires show significant heterogeneity along their lengths for the photocatalytic generation of hydroxyl radicals. Through quantitative, coordinate-based colocalization of multiple probe molecules activated by the same nanowires, we demonstrate that the nanoscale regions most active for the photocatalytic generation of …

Gravity-Drawing Flexible Silicone Filaments As Fiber Optics And Model Foldamers, Katherine Snell

CMC Senior Theses

Here, we present a method of gravity-drawing polydimethylsiloxane (PDMS) silicone fibers with application as fiber optics and as model foldamers. Beginning as a viscous liquid, PDMS is cured using heat until its measured viscosity reaches 4000 mPa•s. The semi-cured elastomer is then extruded through a tube furnace to produce thin (diameters on the order of hundred micrometers) filaments with scalable lengths. PDMS is biocompatible, gas-permeable, flexible, and hydrophobic. Additionally, the PDMS surface hydrophobicity can be modified via UV exposure, O2 plasma, and corona discharge. We demonstrate the patternibility (i.e patterns of hydrophobicity) of PDMS fibers, adding complexity to potential foldamer …

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 …

Study Of Amorphous Boron Carbide And Hydrogenated Boron Carbide Materials Using Molecular Dynamics And Hybrid Reverse Monte Carlo, Rajan Khadka

MSU Graduate Theses

We present a computational study of amorphous boron carbide (a-B_xC) models using Molecular Dynamics (MD) studied with Stillinger-Weber (SW) and ReaxFF potential. The atomic structure factor (S(Q)), radial distribution function (RDF) and bond lengths comparison with other experimental and ab initio models shows that a random arrangement of icosahedra (B₁₂, B₁₁C) interconnected by chains (CCC, CBC) are present in a-B_xC. Afterward, Hybrid Reverse Monte Carlo (HRMC) technique is used to recreate a-B_xC structures. The existing SW potential parameters of Boron are optimized for the α-rhombohedral (Icosahedral B_{12 …}

Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland

Electronic Thesis and Dissertation Repository

Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …

Reactive And Stimuli-Responsive Sulfonium-Based Polymer Zwitterions, Cristiam Santa Chalarca

Doctoral Dissertations

This dissertation describes the synthesis and characterization of novel monomers and (co)polymer zwitterions that incorporate trialkylsulfonium cations. The novel materials presented herein constitute a unique type of polymer zwitterions that exhibit salt- and temperature-dependent water solubility as well as inherent reactivity. The behavior of these polymers in aqueous solutions, as nanostructures, and at liquid-liquid interfaces was studied; in all cases, the inherent reactivity of the polymers was harnessed towards the fabrication of novel polymers and soft materials. Following an introductory chapter, Chapter 2 describes the synthesis of sulfonium sulfonate monomers and polymer zwitterions. Both styrenic and methacrylic monomers were synthesized …

The Development Of An Integrated Simulation Model On Understandings On The Interaction Between Electromagnetic Waves And Nanoparticles, Xiaojin Wang

Masters Theses & Specialist Projects

To investigate the interaction between nanoparticles and electromagnetic waves, a numerical simulation model based on FEM was built in this thesis. Numerical simulation is an important auxiliary research method besides experiments. The optical properties of nanoparticles consist of scattering, absorption, and extinction, and in the case of nanoparticle suspension, the transmission is also involved. This thesis addressed two typical applications based on the established model, one was regarding the nanofluids for solar energy harvesting, and the other was regarding the optical properties of atmospheric soot. In the case of the nanofluids solar energy harvesting, the established model provided a convenient …

An In-Situ Study Of The Aqueous Speciation Of Uranium (Vi) Under Hydrothermal Conditions, Diwash Dhakal

MSU Graduate Theses

Rigorous study of the speciation distribution of uranyl-chloride bearing solutions under hydrothermal conditions is important to understand the transport mechanism of uranium underground, which is of uttermost interest to parties studying the geological uranium deposits and those studying the possibilities of geological repositories for spent nuclear waste. I report an in-situ Raman spectroscopic study of the speciation distribution of aqueous uranyl-chloride complexes upto 500°C conducted using a HDAC as the high PT spectroscopic cell. The samples studied contained the species UO₂²⁺, UO₂Cl⁺, UO₂Cl₂⁰ and UO₂Cl₃^{- …}

Application Of X-Ray Grating Interferometry To Polymer/Flame Retardant Blends In Additive Manufacturing, Omoefe Joy Kio

LSU Doctoral Dissertations

X-ray grating interferometry is a nondestructive tool for visualizing the internal structures of samples. Image contrast can be generated from the absorption of X-rays, the change in phase of the beam and small-angle X-ray scattering (dark-field). The attenuation and differential phase data obtained complement each other to give the internal composition of a material and large-scale structural information. The dark-field signal reveals sub-pixel structural detail usually invisible to the attenuation and phase probe, with the potential to highlight size distribution detail in a fashion faster than conventional small-angle scattering techniques. This work applies X-ray grating interferometry to the study of …

Nmr Characterizations Of Candidate Battery Electrolytes, Stephen A. Munoz

Dissertations, Theses, and Capstone Projects

Enormous strides have been made in next-generation power sources to build a more sustainable society. Energy storage has become a limiting factor in our progress, and there are huge environmental and financial incentives to find the next step forward in battery technology. This work discusses NMR methods for characterizing materials for use in battery application, with a special focus on relaxometry and diffusometry. Examples are provided of various recent investigations involving novel candidate electrolyte materials with different collaborators. Works discussed in this thesis include: the characterization of a new disruptive solid polymer electrolyte technology, investigations of the dynamics of super …

Effects Of High Pressure On Photochemical Reactivity Of Organic Molecular Materials Probed By Vibrational Spectroscopy, Jiwen Guan

Electronic Thesis and Dissertation Repository

Chemical transformations of molecular materials induced by high pressure and light radiation exhibit novel and intriguing aspects that have attracted much attention in recent years. Particularly, under the two stimuli, entire transformations of molecular species can be realized in condensed phases without employing additional chemical constraints, e.g., the need of solvents, catalysts or radical initiators. This new synthetic approach in chemistry therefore satisfies increasing need for production methods with reduced environmental impacts. Motivated by these promises, my Ph. D thesis focuses on this state-of-the-art branch of high-pressure photochemistry. Specifically, high pressure is employed to create the necessary reaction conditions to …

Molecular Assembly Of Monolayer-Protected Gold Nanoparticles And Their Chemical, Thermal, And Ultrasonic Stabilities, Steven Ray Isaacs

Masters Theses & Specialist Projects

Gold monolayer-protected nanoclusters (MPCs) with average diameters of 1-5 nm protected by alkane- and arenethiolates were synthesized. Mixed-monolayer protected nanoparticles (MMPCs) were prepared by functionalizing hexanethiolate-protected MPCs with either 11-mercaptoundecanoic acid (MUA-MMPC), 11-mercaptoundecanol (MUO-MMPC), or 4-aminothiophenol (ATP-MMPC) using ligand place exchange. Presentation of various chemical reagents such as nucleophile, acid, or base and change in physical environment through ultrasonic and thermal irradiation resulted in changes to particles and their physical properties. Thermogravimetric analysis (TGA) was used to measure maximum temperature of the derivated thermogravimetric peaks (Tmax,DTG) as a means of comparing temperature dependence of mass loss. The absorption spectrum within …