The characteristics of a pulsed laser ion source have been studied. A pulse from a heating laser (Nd: YAG laser) desorbs the neutral atoms from the surface of a metal target and then a second pulse or pulses from excimer or dye lasers selectively ionize the desorbed neutrals using the Resonance Ionization Spectroscopy technique. Time-of-flight and electrostatic energy analyzer measurements have been used to study different characteristics of this ion source such as spatial, velocity, and energy distributions. These measurements reveal that although the energy spread of the basic source is relatively high, (FWHM $ sim$ 37 eV) the use of a pulsed acceleration system can reduce this spread by a factor of 5 (to about 7 eV), making the source suitable for collinear laser spectroscopy.

This thesis presents a theoretical approach to Ostwald ripening of droplets in arbitrary dimensions. A mean-field theory is constructed to incorporate screening effects among the competing droplets. The mean-field equations are solved to all orders in the volume fraction to provide analytic expressions for the coarsening rate, the droplet distribution function, and the time-dependent droplet number. These results are in agreement with experiments in three-dimension and with very large scale and extensive numerical studies in both two and three dimensions undertaken in this thesis. The numerical study also provides the time evolution of the structure factors, wherein lengths scale with the average droplet radius. Finally, the mean-field theory is extended to exciton systems and surfactant systems.

The spin-lattice relaxation rate R$ sb1$ of irradiated Fricke solution was studied as a function of the absorbed dose D. The R$ sb1$ increases linearly with D up to a dose of $ sim$250 Gy after which the response saturates. A model describing the R$ sb1$ of a solution of either ferrous (Fe$ sp{2+})$ or ferric (Fe$ sp{3+})$ ions is presented; it is based on fast exchange between protons on water molecules in the bulk and protons on water molecules in the coordination shell of the ions. All inherent relaxation parameters of the different proton groups are determined. An extension of the model is made to describe the spin-lattice relaxation behaviour of irradiated Fricke solution. Good agreement between model predictions and experimental results is observed. The model relates the spin-lattice relaxation rate of a Fricke dosimeter to the chemical yield of ferric ion, thus creating an absolute dosimetry technique. Various practical aspects of the NMR-Fricke system are described.

The equilibrium properties of polymers end-grafted to an impenetrable interface, the "polymer brush", are investigated. Relevant concepts and techniques of statistical polymer physics are discussed; in particular, a simulation technique that is very efficient for studying polymer brushes is introduced. This technique is demonstrated through simulations of a well characterized polymer brush system. The results of original investigations of phase separation in polymer brushes are also presented. An instability in the lateral monomer density of a polymer brush is observed under sufficiently poor solvent conditions. The onset of this instability is found to agree with a previous prediction. A compositional instability is found in the lateral densities of a two-component polymer brush under conditions of sufficient immiscibility between the two components. The effects of varying solvent conditions are considered. Finally, the onset of the compositional instability is determined using the technique of the self consistent mean field, and the results compared to simulation.

A dual-wavelength Scanning Near-Field Optical Microscope was developed in order to investigate near-field contrast mechanisms as well as biological samples in air. Using a helium-cadmium laser, light of wavelengths 442 and 325 nanometers is coupled into a single mode optical fiber. The end of the probe is tapered to a sub-wavelength aperture, typically 50 nanometers, and positioned in the near-field of the sample. Light from the aperture is transmitted through the sample and detected in a confocal arrangement by two photomultiplier tubes. The microscope has a lateral topographic resolution of 10 nanometers, a vertical resolution of 0.1 nanometer and an optical resolution of 30 nanometers. Two alternate methods of producing the fiber probes, heating and pulling, or acid etching, are compared and the metal coating layer defining the aperture is discussed. So-called "shear-force" interactions between the tip and sample are used as the feedback mechanism during raster scanning of the sample. An optical and topographic sample standard was developed to calibrate the microscope and extract the ultimate resolution of the instrument. The novel use of two wavelengths enables the authentication of true near-field images, as predicted by various models, as well as the identification of scanning artifacts and the deconvolution of often highly complicated relationships between the topographical and optical images. Most importantly, the use of two wavelengths provides information on the chemical composition of the sample. Areas of a polystyrene film are detected by a significant change in the relative transmission of the two wavelengths with a resolution of 30 nanometers. As a biological application, a preliminary investigation of the composition of Black Spruce wood cell fibers was performed. Comparisons of the two optical channels reveal the expected lignin distributions in the cell wall.

<p> The meta-GGA functionals and random phase approximation are tested for phase transitions and a strongly correlated transition metal oxide in this dissertation. One of the latest meta-GGA functionals is also employed to study the van der Waals bound system in surface science. Our main purpose is to reveal the performance of new exchange-correlation functionals on various properties and systems. We are also interested in seeking the possible relationship between the performance of a semilocal functional and its exchange enhancement factor.</p><p> We have studied the structural phase transitions in crystalline Si (insulator to metal), SiO₂ (insulator to insulator) and Zr (metal to metal) systems, as a test of exchange energy semilocal functionals on Jacob's ladder. Our results confirm the energy-geometry delimma of GGAs in three systems. The most sophisticated non-empirical meta-generalized gradient approximations (meta-GGAs) such as TPSS (Tao-Perdew-Staroveov-Scuseria) and revTPSS (revised TPSS) give better lattice constants than PBE, but the phase transition parameters (energy difference and transition pressure) are smaller and less realistic than those from the latter GGA. However, the recent functionals of meta-GGA made simple family (MGGA_MS) behave differently to those previous meta-GGAs, predicting larger and more realistic phase transition parameters. Meanwhile, MGGA_MS also delivers the equilibrium geometry of crystalline materials similar to previous non-empirical meta-GGAs.</p><p> In contrast to semilocal functionals, the nonlocal functionals such as the range-separated hybrid functional HSE06 (Heyd-Scuseria-Ernzerhof) and non-self consistent random phase approximation (RPA) are not only able to give the accurate equilibrium geometry , but also predict the realistic phase transition parameters for Si and SiO₂ systems.</p><p> The ground state of rutile-type vanadium dioxide (R-VO₂) represents a great challenge to the current density functional theory. In this dissertation, we investigated the electronic structures and magnetism of R-VO₂ using exchange-correlation functionals of all five rungs on Jacob's ladder. Our calculations show that all semilocal functionals (LSDA, GGAs and meta-GGAs) and hybrid functionals (HSE06) stabilize the spin-polarized states (ferromagnetic and anti-ferromagnetic states) over non-magentic state, which are completely opposite to experimental observation. Suprisingly, LSDA gives the best energetic descriptions for magnetic and non-magnetic phases of R-VO₂ among semilocal functionals and HSE06. Othwerwise, RPA calculations are highly dependent on the inputs in the spin polarized case. With PBE inputs, RPA also fails, giving lower energies for spin-polarized states than for the non-magnetic phase. Meawhile, the results are reversed using LSDA inputs. From the computed equilibrium cell volume, we observe the error cancellation in the exchange-correlation hole of most semilocal functionals in the spin-polarized calculations. LSDA and RPA do not fit to this picture. By analyzing the local magnetic moments of vanadium atoms, it is found that the magnetic property predicted from meta-GGA can be related to its exchange enhancement factor.</p><p> The physisorption of a molecule on a transition metal surface is also another difficult problem in DFT because of the long-range van der Waals interactions. The recently developed MGGA_MS family of density functionals is able to capture a portion of intermediate range dispersion interactions. Therefore, we employed MGGA_MS2 to study the physisorption of CO₂ on Pt (111) surface, and the results are compared to those of PBE, PBE+D2 and optB88-vdW methods. The computed binding curves comfirm that that MGGA_MS2 indeed captures the van der Waals interactions near the equilibrium binding distance, and the obtained binding distance is also in good agreement with PBE+D2 and optB88-vdW calculations. By computing the electron density difference map (EDDM), we find that the electron densities of CO₂ and Pt (111) surface are strongly polarized in optB88-vdW, creating the dipole moments in two subsystems. Such effect is reduced in MGGA_MS2. For PBE, the polarization of electron density is very weak, but not negligible. The &agr; dependence in the exchange enhancement factor of a meta-GGA is the key to capture the intermediate range van der Waals interactions.</p><p> In summary, a meta-GGA functional can step out of the famous "energy-geometry dilemma" , predicting good lattice constants and phase transition parameters at the same time. With the proper construction, a meta-GGA can even capture a portion of van der Waals interactions. The RPA is usually more accurate than semilocal functionals for many ground state properties. The strongly correlated systems like R-VO₂ are still a big challenge to present-day density functional theory. We will continue to seek more accurate exchange-correlation functionals.</p>

<p> This thesis investigates the fundamental nanoscale near-field light matter interaction between a probe tip and plasmonic antenna nanostructures. The thesis is focused on polarization control of metallic plasmon modes using scattering-type scanning near-field optical microscopy (s-SNOM). Part of the thesis is dedicated to spectroscopic near-field comparison of coated and bare single plasmonic particles in the infrared wavelength range (&lambda;= 9&ndash;11 &micro;m) using s-SNOM. By tuning the wavelength of the incident light, we have acquired information on the spectral polarization dependence plasmon modes and plasmon/phonon&ndash;polariton resonant near-field interactions. The enhanced near-field coupling between the probe tip and high index Au nanostructures and Au-core thin silica coating (thickness &ap;10 nm) is described and quantified. </p>

<p> InAs/GaSb superlattices are a material system well suited to growth via molecular beam epitaxy. The ability to tune the band gap over the entire mid and long wave infrared spectrum gives a large number of applications for devices made from InAs/GaSb superlattice material. The growth of high quality InAs/GaSb superlattice material requires a careful study of the parameters used during epitaxial growth. This work investigates the growth of tunnel junctions for InAs/GaSb based superlattice light emitting diodes, the presence of defects in GaSb homoepitaxial layers, and variations in the growth rate of InAs/GaSb superlattice samples. Tunnel junctions in cascaded structures must provide adequate barriers to prevent carriers from leaking from one emission region to the next without first recombining radiatively, while at the same time remain low in tunneling resistance for current recycling. A variety of tunnel junction designs are compared in otherwise identical four stage InAs/GaSb superlattice light emitting diodes, which past studies have found hole confinement to be problematic. GaSb was used on the p-side of the junction, while various materials were used on the n-side. Al0.20In0.80As0.73Sb0.27 tunnel junctions function best due to the combination of favorable band alignment and ease of growth. Pyramidal defects have been observed in layers of GaSb grown by molecular beam epitaxy on GaSb substrates. These defects are typically 3-8 nanometers high, 1-3 microns in diameter, and shaped like pyramids. Their occurrence in the growth of GaSb buffer layers can propagate into subsequent layers. Defects are nucleated during the early stages of growth after the thermal desorption of native oxide from the GaSb substrate. These defects grow into pyramids due to a repulsive Ehrlich-Schwoebel potential on atomic step edges leading to an upward adatom current. The defects reduce in density with growth of GaSb. The insertion of a thin AlAsSb layer into the early stages of the GaSb buffer increases the rate of elimination of the defects, resulting in a smooth surface within 500nm. The acceleration of defect reduction is due to the temporary interruption of step-flow growth induced by the AlAsSb layer. This leads to a reduced isolation of the pyramids from the GaSb epitaxial layer, and allows the pyramidal defects to smooth out. Investigations into varying the superlattice growth rate have not been reported widely in the literature. Due to the frequent use of soaks, growth interrupts, and other interface structuring steps the superlattice growth rate and the interface layer sequence are linked. In order to properly study the effects of growth rate variations and interface design changes it is necessary to account for the effect on growth rate due to the interfaces. To this end it is useful to think of the effective growth rate of the superlattice, which is the total layer thickness divided by the total time, per superlattice period. Varying the effective growth rate of superlattice photoluminescence samples shows a peak in output at ~0.5 monolayers per second. Investigations into the structural properties of the superlattices show no decrease in structural uniformity for effective growth rates up to ~1.4 monolayers per second.</p>

The flow of a two-dimensional incompressible non-Newtonian fluid, showing a viscoelastic behavior, has been studied using the White-Metzner model with a phenomenological law for the viscosity, the Spriggs' truncated power-law model. Our goal was to determine if these models could generate the oscillating instabilities appearing in such fluids at very high driving force. We studied the effect of various quantities on the time-dependent numerical simulations and noticed that the mesh length was not very important for the accuracy of the results. However, the time constant modulus appearing in the White-Metzner model and the applied pressure were of paramount importance for the relaxation time of a disruptive flow. / We thus showed that this model was effective only at low pressure and that without adding new aspects to the study of the flow, such as compressibility, we could not obtain any oscillating flow at high pressure. Despite this fact, exact steady-state solutions, as well as a time-dependant solution in the case of very small Reynolds number ($R to$ 0), have been given.

Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006. / Source: Dissertation Abstracts International, Volume: 68-02, Section: B, page: 1018. Adviser: Richard L. Weaver. Includes bibliographical references (leaves ) Available on microfilm from Pro Quest Information and Learning.