A novel method to detect and quantify the growth of the solid electrolyte interphase (SEI) on battery electrode materials using in-situ spectroscopic ellipsometry (SE) is presented. The effects of additives in 1 M LiPF6/EC:DEC (1:2) electrolyte on the SEI were studied. Thin film electrodes of a-Si, Ni, and TiN were prepared by magnetron sputtering for use with a custom-designed tubular in-situ electrochemical cell. Li/a-Si and Li/Ni in-situ cells in 0.1 M LiPF6/EC:DEC (1:2) were studied by galvanostatic chronopotentiometry. Large changes in the ellipsometric parameters, ? and ?, were observed for both materials. These changes were closely related to the state of charge of the in-situ cell. The formation of an a-LixSi alloy, the formation of an SEI layer, or both contributed to these large changes for a Li/a-Si in-situ cell. For a Li/Ni in-situ cell, a thin transparent surface layer was observed. The surface layer, presumably made from SEI species and species from the displacement reaction between NiO and Li, increased to roughly 17 nm during the first discharge. During the first charge, the surface layer thickness decreased to roughly 5.5 nm and could not be removed, even at high potentials. The effect of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives on SEI formation were studied using a Li/TiN in-situ cell in 1 M LiPF6/EC:DEC (1:2) by potentiostatic chronoamperometry. SEI thicknesses for cells containing no additives, VC, and FEC were roughly 18 nm, 25 nm and 30 nm, respectively, after a 10 h hold at 0.1 V. SE is a useful technique for measuring thin film growth in-situ on electrode materials for Li-ion batteries.

Thesis (M.S.)--California Polytechnic State University, 2009. / The letter x is subscripted in the title. Title from PDF title page; viewed on October 23, 2009. Major professor: Dr. Richard Savage. "Presented to the faculty of California Polytechnic State University, San Luis Obispo." "In partial fulfillment of the requirements for the degree [of] Master of Science in Materials Engineering." "September 2009." Includes bibliographical references (p. 115-121). Also available on microfiche.

Thesis (Ph.D.)--Ohio University, June, 2005. / Title from PDF t.p. Includes bibliographical references (p. 221-234)

Made available in DSpace on 2014-06-11T19:25:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-09-26Bitstream added on 2014-06-13T20:14:04Z : No. of bitstreams: 1 gatto_fr_me_rcla.pdf: 2278146 bytes, checksum: 259aa88d558d0ea43e1fa7eb8572dd83 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Com a finalidade de possuir um equipamento para determinar o índice de refração de xerogéis e a espessura de filmes finos preparados em nosso laboratório por técnica sol-gel, optamos pela construção de um sistema capaz de determinar a intensidade de luz refletida por uma amostra em função do ângulo de incidência, com controle do estado de polarização da componente incidente e monitoramento da polarização da componente refletida. Dessa forma temos um equipamento capaz de determinar o ângulo de Brewster e assim o índice de refração da amostra em estudo. O equipamento também permite identificar o estado de polarização da luz refletida (luz linearmente, elipticamente e circularmente polarizada) para diversos ângulos de incidência, constituindo assim um Elipsômetro. O sistema é composto de um suporte de amostra e um braço suporte do detector de luz, com movimento de rotação síncrono na razão amostra detector de f para 2f . Todo o mecanismo de acionamento dos motores de passo e aquisição de dados é controlado através das portas paralelas de um computador. A aquisição de dados é feita através de um Conversor Analógico Digital O software de controle dos motores e aquisição de dados foi desenvolvido em linguagem Basic em modo DOS. / With the purpose of possessing an equipment to determine the index of xerogels refraction and the thickness of prepared fine films in our laboratory for technical sun-gel, we opted for the construction of a system capable to determine the light intensity contemplated by a sample in function of the incidence angle, with control of the state of polarization of the incident component and accompaniment of the polarization of the reflected component. In that way we have equipment capable to determine the angle of Brewster and like this the index of refraction of the sample in study. The equipment also allows identifying the state of polarization of the reflected light (it shines lineally, elliptical and circularly polarized) for several incidence angles, constituting like this an Ellipsometer. The system is composed of a sample support and an arm supports of the light detector, with synchronous rotation movement in the detecting of f reason sample for 2f . The whole mechanism of action of the step motors and acquisition of data is controlled through the parallel doors of a computer. The acquisition of data is made through an Analog-to-digital Converter. The software of control of the motors and acquisition of data was developed in language Basic in way DOS.

Descreve-se detalhadamente a teoria e construção de um fotoelasticímetro, destinado ao estudo da estrutura de cristais iônicos deformados pela adição de impurezas. No método utilizado, a modificação do estado de polarização da luz pela amostra é investigada com o auxílio da modulação do feixe por uma placa fotoelástica. Exemplos de aplicação são apresentados. / The theory and construction of a photoelasticimeter are described in detail. The main use of the instrument will be in the study of the structure of ionic crystals deformed by the addition of impurities. In the employed method, the modification of the state of polarization of the light by the sample is investigated with the aid of a photoelastic board. Some examples of use are presented.

Doctor of Philosophy / Department of Physics / Bruce M. Law / We have studied two critical binary liquid mixtures in the mixed phase regime with x-ray and neutron reflectometry to verify universal critical scaling at a non-critical interface. We compared our results with previous results obtained with ellipsometry. At a solid-liquid or liquid-vapor interface of an AB binary liquid mixture the component with the lower surface tension will dominate that interface. If the surface tension differential between the components of the mixture is large enough the composition of the surface layer will loose its dependence on. This case is referred to as strong adsorption. We study the case of strong adsorption for a binary liquid mixture at the critical composition with respect to the demixing phase transition. Sufficiently close to the critical temperature Tc the influence of bulk critical behavior is expected to dominate the way the surface adsorption layer decays with depth z from the surface composition to the bulk composition. The length scale of the decay profile is expected to be proportional to the composition correlation length, and is expected to scale with a universal composition scaling function. In a neutron reflectometry study of a critical mixture of D2O and 3-methylpyridine against a quartz substrate we verify universal critical scaling using a scaling function previously used to describe ellipsometry data. In an x-ray reflectometry study of the liquid-vapor interface of a critical mixture of n-dodecane and 1,1,2,2 tetrabromoethane, which had previously been studied with ellipsometry, we find that we are able to describe all data by using the same scaling function provided that we account for non-critical, system dependent surface structure as well. We are also able to simulate ellipsometry with our mathematical profile model and compare the simulation to the previous ellipsometry data.

Master of Science / Department of Physics / Bruce M. Law / With advances in micromechanical machining and nanotechnology, the sample volume needed for biological research and other analysis decreases. With small volume, sample-surface interactions including adsorption must be considered. These adsorption effects can be observed by analyzing light reflected from the solid-liquid interface, and the contact angle of a solution on the surface. Presented is the design and construction of an ellipsometer, a device used to analyze light reflected off of a solid-liquid interface to find interfacial properties, including thickness of a thin film formed by adsorption. The taq enzyme is shown to have a large change in contact angle from seventy degrees to about ten degrees over a short (ten minute) time period when placed on an SU-8 substrate, indicating a change in energy at the interface and a large amount of adsorption. Silane substrates are found to produce similar results. Ellipticity of a colloidal gold nanoparticle solution on a glass substrate is also observed, whose results are difficult to interpret due to bulk shifts in the sample. With the ellipsometer running correctly, it can be used for a number of experiments, including spectroscopic ellipsometry and Brewster angle microscopy, with some modifications.

Absorption of octadecanethiol and p-nitrobenzenethiol onto gold surfaces from ethanol solutions has been studied by means of contact angle, optical ellipsometry, angle-resolved XPS (ARXPS), and with grazing angle total reflection FTIR. Growth of the monolayers from dilute solutions has been monitored and Langmuir isotherm adsorption curves were fitted to experimental data. A saturated film is formed within approximately 5h after immersion in solutions of concentrations ranging from 0.0005mM to 0.01mM. We found, that the final density of monolayer depends on the concentration of the solution.

Wurtzite III-nitride semiconductor materials have many technically important applications in optical and electronic devices. As GaN-based visible light-emitting diodes (LEDs) and lasers starts to mature, interest in developing UV devices starts to rise. The search for materials with larger bandgaps and high refractive index contrast in the UV range has inspired multiple studies of BN-based materials and their alloys with traditional III-nitrides. Additionally, alloying III-nitrides with boron can reduce their lattice parameters giving a new option for strain engineering and lattice matching. In this work I investigate the refractive indices of BAlN and BGaN over the entire compositional range using hybrid density functional theory (DFT). An interesting non-linear trend of the refractive index curves appears as boron content is increased in the BAlN and BGaN alloys. The results of this calculation were interpolated and plotted in three dimensions for better visualization. This interpolation gives a 3D dataset that can be used in designing a myriad of devices at all binary and ternary alloy compositions in the BAlGaN system. The interpolated surface was used to find an optimum design for a strain-free, high reflection coefficient and high bandwidth DBR. The performance of this DBR was quantitatively evaluated using finite element simulations. I found that the maximum DBR reflectivity with widest bandwidth for our materials occurs at a lattice parameter of 3.113 Å using the generated 3D dataset. I use the corresponding material pair to simulate a DBR at the wavelength 375 nm in the UVA range. A design with 25 pairs was found to have a peak reflectivity of 99.8%. This design has a predicted bandwidth of 26 nm measured at 90% peak performance. The high reflectivity and wide bandwidth of this lattice-matched design are optimal for UVA VCSEL applications. I have assisted in exploring different metalorganic chemical vapor deposition (MOCVD) techniques, continuous growth and pulsed-flow modulation, to grow and characterize BAlN alloys. Samples grown using continuous flow show better optical quality and are characterized using spectroscopic ellipsometry. The refractive index of samples obtained experimentally is significantly below the predicted value using DFT.

<p>In the realm of tunable optical devices, 3D nanostructures with metals and dielectrics have been utilized in a wide variety of practical applications ranging from optical switching to beam-steering devices. 2D materials, on the other hand, have enabled the exploration of truly new physics unattainable with 3D systems due to quantum confinement leading to unique optical properties and enhanced light-matter interactions. Transdimensional materials (TDMs) – atomically thin films of metals – can couple the robustness of 3D nanostructures with the new physics enabled by 2D features. However, the evolution of the optical properties in the transdimensional regime between 3D and 2D is still underexplored. The optical properties of metallic TDMs are expected to show unprecedented tailorability, including strong dependences on the film thickness, composition, strain, and surface termination. They also have an increased sensitivity to external optical and electrical perturbations, owing to their extraordinary light-confinement. Additionally, the small atomic thicknesses may lead to strongly confined surface plasmons and quantum and nonlocal phenomena. The strong tunability and light-confinement offered by TDMs have resulted in a search for atomically thin plasmonic material platforms that facilitate active metasurfaces with novel functionalities in the visible and near infrared (NIR) range. In this research, we explore the plasmonic properties and tailorability of atomically thin titanium nitride (TiN). We experimentally and theoretically study the thickness-dependent optical properties of epitaxial TiN films with thicknesses down to 1 nm to demonstrate confinement induced optical properties. Overall, this research demonstrates the potential of TDMs for unlocking novel optical phenomena at visible and NIR wavelengths and realizing a new generation of atomically thin tunable nanophotonic devices. </p>