Browsing by Author "Ritter, Alfred L."
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- Casimir Force in Non-Planar Geometric ConfigurationsCho, Sung Nae (Virginia Tech, 2004-03-22)The Casimir force for charge-neutral, perfect conductors of non-planar geometric configurations have been investigated. The configurations were: (1) the plate-hemisphere, (2) the hemisphere-hemisphere and (3) the spherical shell. The resulting Casimir forces for these physical arrangements have been found to be attractive. The repulsive Casimir force found by Boyer for a spherical shell is a special case requiring stringent material property of the sphere, as well as the specific boundary conditions for the wave modes inside and outside of the sphere. The necessary criteria in detecting Boyer's repulsive Casimir force for a sphere are discussed at the end of this thesis.
- Construction of an Optical Quarter-Wave Stack Using the ISAM (Ionic Self-Assembled Multilayers) TechniquePapavasiliou, Kriton (Virginia Tech, 2010-07-09)The purpose of this thesis is to make a broadband antireflection coating configuration known as a quarter-wave stack consisting of one layer of titania and of one layer of silica nanoparticles. We utilize much that is already known about silica nanoparticle deposition. The first objective of this thesis is deposition and characterization of titania nanoparticle films deposited on glass microscope slides by a technique known as Ionic Self-Assembled Multilayers or ISAM deposition. This technique takes advantage of the electrostatic attraction between oppositely charged materials and ideally results in a uniform nanoparticle film whose thickness and optical properties can be tightly controlled. Deposition of a quarter-wave stack based on ISAM deposition of silica and titania nanoparticles is significantly simpler and less expensive than alternative deposition methods. Initial attempts to deposit titania films were unsuccessful because of excess diffuse scattering due to inhomogeneities in the film. In order to reduce diffuse scattering, two approaches were considered. The first approach was to improve the deposition process itself by experimenting with different values of deposition parameters such as solution pH and solution molarity. The other approach focused on removing the large nanoparticle aggregates from the colloidal solutions of titania nanoparticles that were suspected to be responsible for rough film surfaces resulting in diffuse scattering. This approach was successful. In addition, evidence suggested that surface roughness contributed more to diffuse scattering than the bulk of the films. After minimizing diffuse scattering from titania nanoparticle films, we used known results from research on silica nanoparticle films to deposit quarter-wave stacks consisting of one layer of titania nanoparticles with high refractive index and one layer of silica nanoparticles with low refractive index. This contrast in refractive indices is a desirable characteristic of quarter-wave stacks. The thicknesses and refractive indices of the two layers in the quarter-wave stacks were measured by ellipsometry and compared to the nominal thicknesses of these layers. Finally, the reflectance was derived from a model of the quarter-wave stack and was compared to the measured reflectance. It was found that construction of a quarter-wave stack by ISAM is possible but that it will be necessary to acquire data from more experiments.
- Dielectric properties of PFN-PFT solid solution synthesized by the molten salt methodAmanuma, Kazushi (Virginia Tech, 1991-08-09)Various compositions of PFN-PFT solid solution were synthesized by the molten salt method at 800°C and 900°C. Higher temperature was necessary to form pure perovskite of PFT than PFN. However, those synthesized at higher temperatures tended to decompose during sintering. The particle size was not uniform and increased from PFT to PEN. The distribution of grain size in the sintered pellets was bi-modal. The grain size increased as the particle size increased. Those synthesized at 900°C had quite a different behavior from those synthesized at 800°C during sintering. Each composition of PFN-PFT system showed a broad dielectric phase transition in the different temperature range. This behavior was well described by the statistical model of compositional fluctuation.
- Differential algebraic methods for obtaining approximate numerical solutions to the Hamilton-Jacobi equationPusch, Gordon D. (Virginia Tech, 1990)I present two differential-algebraic (DA) methods for approximately solving the Hamilton- Jacobi (HJ) equation. I use the “automatic differentiation” property of DA to convert the nonlinear partial-differential HJ equation into a initial-value problem for a DA-valued first-order ordinary differential equation (ODE), the “HJ/DA equation”. The solution of either form of the HJ/DA equation is equivalent to a perturbative expansion of Hamilton’s principle function about some reference trajectory (RT) through the system. The HJ/DA method also extracts the equations of motion for the RT itself. Hamilton’s principle function generates the canonical transformation, or mapping, between the initial and final state of every trajectory through the system. Since the map is represented by a generating function, it must automatically be symplectic, even in the presence of round-off error. The DA-valued ODE produced by either form of HJ/DA is equivalent tc a hierarchically-ordered system of real-valued ODEs without “feedback” terms; therefore the hierarchy may be truncated at any (arbitrarily high) order without loss of self consistency. The HJ/DA equation may be numerically integrated using standard algorithms, if all mathematical operations are done in DA. I show that the norm of the DA-valued part of the solution is bounded by linear growth. The generating function may be used to track either particles or the moments of a particle distribution through the system. In the first method, all information about the perturbative dynamics is contained in the DA-valued generating function. I numerically integrate the HJ/DA equation, with the identity as the initial generating function. A difficulty with this approach is that not all canonical transformations can be represented by the class of generating functions connected to the identity; one finds that with the required initial conditions, the generating function becomes singular near caustics or foci. One may continue integrating through a caustic by using a Legendre transformation to obtain a new (but equivalent) generating function which is singular near the identity, but nonsingular near the caustic. However the Legendre transformation is a numerically costly procedure, so one would not want to do this often. This approach is therefore not practical for systems producing periodic motions, because one must perform a Legendre transformation four times per period. The second method avoids the caustic problem by representing only the nonlinear part of the dynamics by a generating function. The linearized dynamics is treated separately via matrix techniques. Since the nonlinear part of the dynamics may always be represented by a near-identity transformation, no problem occurs when passing through caustics. I successfully verify the HJ/DA method by applying it to three problems which can be solved in closed form. Finally, I demonstrate the method’s utility by using it to optimize the length of a lithium lens for minimum beam divergence via the moment-tracking technique.
- Dual Processing Spatially Distributed Integrating Fiber Optic Sensors for Non-intrusive Patient MonitoringXu, Xiaohua (Virginia Tech, 2005-04-21)Given the rapid aging of the worldâ s population, improvements in technology for automation of patient care and documentation are badly needed. This project is based on previous research that demonstrated a â smartâ bed that can non-intrusively monitor a patient in bed and determine a patient's respiration, heart rate and movement without intrusive or restrictive medical measurements. The â smartâ bed is an application of spatially distributed integrating fiber optic sensors. The basic concept is that any patient movement that also moves an optical fiber within a specified area will produce a change in the optical signal. A statistical mode (STM) sensor and a high order mode excitation (HOME) sensor were previously investigated, based on which the author developed the present design including both modal modulation approaches. Development was made in both hardware and software for the combined STM/HOME sensor: a special lens system was installed allowing only the high order modes of the optical fiber to be excited and coupled into the sensor; computer-processing method was used for handling output from the dual STM-HOME sensor, which would offer comprehensive perturbation analysis for more reliable patient monitoring. Experimental results of simulating human body breathing and heartbeats by periodic mechanical perturbations are also presented, and the relative advantage and drawbacks of the two modal modulation approaches are discussed.
- (e, 2e) spectrometer for investigating the spectral momentum density of thin-filmsRitter, Alfred L.; Dennison, John Robert; Dunn, J. (AIP Publishing, 1984-08)An (e, 2e) spectrometer has been constructed for detecting scattered and recoiling electrons from a thin solid film. The cross section for observing the two electrons in coincidence is proportional to the spectral momentum density of the target. In this spectrometer the energy of the incident electron beam is 25 keV and the beam current is approximately 40 μA. The energy resolution (FWHM) is ≤4 eV. The momentum resolution (FWHM) can be varied from 0.2 to 1.0 Å− 1. Preliminary coincidence data from an amorphous carbon film are presented.
- Effects of Thickness, Morphology and Molecular Structure of Donor and Acceptor Layers in Thermally Interdiffused Polymer PhotovoltaicsGopal, Anamika (Virginia Tech, 2007-04-10)An in-depth study of concentration gradients in thermally-interdiffused polymer – fullerene photovoltaic devices, with a focus on thickness and heat treatments, is presented in this thesis. Device performance is improved from the bilayer by the creation of a concentration gradient of the donor and acceptor materials throughout the active layer of the device. Concentration gradients are expected to improve device performance by optimizing the charge transfer, transport and collection processes. This is achieved through heat-induced interdiffusion of the two materials at temperatures above the glass transition temperature of the polymer. Investigation of the poly(3-octylthiophene) (P3OT) – C₆₀ system show a three-fold improvement in the external quantum efficiencies (EQE) as compared with bilayer devices. Auger spectroscopy, combined with argon-ion beam milling, serves to record the concentration depth profile and identify concentration gradients in the device through detection of the sulfur in the P3OT backbone. Concentration gradients are optimized to yield the best devices through a thickness variation study conducted on the P3OT – C₆₀ system for fixed thermal interdiffusion conditions at 118 °C for 5 minutes. An optimum thickness of 40 to 60 nm is obtained for the two materials that yields the ideal morphology of a concentration gradient as recorded by Auger spectroscopy. For such devices, the concentration gradient is seen to extend through the device, ending in a thin layer of pure material at each electrode. A monochromatic power conversion efficiency of 2.05% is obtained for 5.3 mW/cm²⁺ illumination at 470 nm. A brief study is also presented to optimize the concentration gradient profile through variations of the thermal parameters. The dependence of the concentration gradient on the interdiffusion time and temperature is investigated. The merits of heat treatment on the crystallinity of P3OT and the overall device performance are also discussed. It is shown in some case that devices with annealed P3OT layers show almost twice the EQE as non-annealed P3OT layer devices. Potential alternatives for C₆₀ in interdiffused devices with P3OT have been presented. [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM), a well-investigated acceptor for blend devices, is studied as an acceptor in concentration gradient devices. A method for spin-coating uniform bilayers of P3OT and PCBM, without solution damage to either layer, is presented. A thermal variation study of the interdiffusion conditions on this system indicated higher interdiffusion temperatures and times are preferred for P3OT – PCBM systems. For interdiffusion at 150 °C for ten minutes, EQE values approaching 35 % at 500 nm are obtained. Auger spectroscopy studies on this system yielded the same conclusions about the concentration gradient device morphology that gives optimum device output. 1:1 and 1:2 blends of P3OT – PCBM are also studied. The influence of various thermal treatments on these devices is described. The endohedral fullerene Sc₃N@C₈₀ is introduced as a new acceptor material. The endohedral fullerene consists of Sc₃N cluster enclosed in a C₈₀ cage. An order of magnitude increase is seen in device performance upon sublimation of these molecules on a P3OT layer confirming its effectiveness as an acceptor. Preliminary studies done on this system indicated the need for greater thermal treatment to produce optimum concentration gradients. An in depth study for varying temperatures and times is presented. The best device performance was seen for interdiffusion at 160 °C for 25 minutes. The endohedral fullerene devices also show a long-term deterioration and so best result are presented from a set of devices fabricated within the same time period. The study of these three donor-acceptor systems confirms that the conclusions on the thickness dependence and device performance study conducted for the P3OT – C₆₀ system extend to other acceptors. A model of EQE for varying thicknesses based on absorption in the interdiffused concentration gradient regions is also presented. This model effectively highlights the influence of P3OT layer thickness on the trends observed in the EQE. It did not, however, reproduce the experimental thickness variation results for varying C₆₀ thicknesses. Incorporation of the effects of the electric field intensity distribution is expected to correct for this. Suggestions have been given on how this might be achieved.
- Electron-energy-loss and optical-transmittance investigation of Bi2Sr2CaCu2O8Wang, Y. Y.; Feng, G. F.; Ritter, Alfred L. (American Physical Society, 1990-07)The energy-loss function Im(-1/ε) of Bi2Sr2CaCu2O8 has been measured over the range Eloss=0.8 to 80 eV by transmission electron-energy-loss spectroscopy (EELS) (nonimaging). The energy and momentum resolution were 0.1 eV and 0.04 Å-1, respectively. The low-energy spectra (Eloss≤3 eV) were studied as a function of momentum transfer (0.1 Å-1≤q≤0.3 Å-1). A well-defined peak in the loss function at Eloss∼1 eV is observed to disperse with momentum proportional to q2. This excitation is analyzed in terms of both an intracell, charge-transfer exciton model and the free-carrier (plasmon) model. The derived effective mass of the exciton mtot/m≃1.0 is far too small for a localized exciton. Using the free-carrier model and random-phase-approximation expressions for the dispersion coefficient, the carrier density and carrier effective mass can be determined separately. From our data and similar measurements by Nücker et al. [Phys. Rev. B 39, 12 379 (1989)], it is found that the effective mass roughly scales with carrier density. A heuristic model is introduced based on the assumption that low-energy gaps exist in portions of the Fermi surface due to structural instabilities. The model suggests how the effective mass could appear to scale with carrier density and why a single Drude term (with frequency-independent effective mass) does not describe the mid- to far-infrared optical spectra. Finally, the optical transmittance of the EELS sample was measured and the spectra analyzed in terms of the free-carrier model.
- The electronic structure of galena and hematite surfaces: applications to the interpretations of STM images, XPS spectra and heterogeneous surface reactionsBecker, Udo (Virginia Tech, 1995-11-07)Scanning tunneling microscopy (STM) images and scanning tunneling spectroscopy (STS) spectra of galena (PbS) and hematite (a-Fe203) were calculated using ab-initio methods in order to interpret experimental images and spectra that were taken in previous studies. These calculations have helped to understand which states of the mineral surfaces were imaged depending on the bias voltage and tip-sample separation. The computational results also gave insight in electron transfer processes that take place during surface adsorption/oxidation/reduction processes. In this context, different oxidation (using O₂ and ferric iron as oxidants) and gold adsorption/reduction mechanisms on galena were evaluated at an atomic level. On hematite, the main emphasis was determining the differences in the local electronic structure of specific sites above the surface and the electronic structure of the bulk. Hereby, step sites turned out to have an increased local density of states at certain electron binding energies that are absent on flat surfaces. states can explain the highly increased reactivity of step sites as compared to terraces. X-ray photoelectron spectra (XPS) were calculated to compare the photoelectron peaks of the calculated specific surface structures (that do not have a bulk equivalent) with experimentally obtained XPS spectra. Most of the calculated peak chemical shifts coincided with those that were found in experiments and that were previously interpreted in terms of known bulk structures. Therefore, it can be inferred that the conventional way of interpreting XPS spectra might be incomplete if specific surface structures are neglected. In order to understand step velocities on a gypsum (010) surface, step energies of different step directions were calculated using an ab-initio approach. An approximately linear relationship was found between the calculated step energies and the experimentally determined step velocities.
- Improvement of the Optical and Mechanical Properties of Silica Nanoparticle Ionic Self-Assembled Multilayer Anti-Reflection Coatings on Glass and Polycarbonate SubstratesRidley, Jason Ian (Virginia Tech, 2010-02-05)This thesis presents the characterization of the optical and mechanical properties of silica nanoparticle films fabricated by ionic self-assembly, also known as layer-by-layer (LbL) deposition. Utilizing electrostatic attraction of oppositely-charged materials permits uniform and rapid growth of the constituents onto planar and curved surfaces. In this work, silica nanoparticles are adsorbed onto glass and polycarbonate substrates, as well as micron-scale glass fibers, with the purpose of improving the optical quality of the respective media. Several methods are presented to improve the adhesion and cohesion of silica nanoparticle films on glass substrates. In the first method, the substrate and nanoparticle surfaces are coated with materials containing sulfonate end groups. Next, a photo-reactive polycation known as diazo-resin (DAR) is used in ISAM deposition with the modified silica nanoparticles. Subsequent exposure to UV converts the ionic bonds between the DAR and sulfonate groups into covalent ones. The second method to improve the mechanical strength is to heat the ISAM silica nanoparticle film at a high enough temperature (500 °C) to remove the polymer and partially fuse the nanoparticles. This technique is known as calcination and is shown to significantly improve the mechanical robustness of the film without compromising the optical properties. The final method involves the deposition of precursor and capping polymer layers around bulk silica nanoparticle films with both bilayer and quadlayer designs. The addition of these polymer layers improves the surface contact between adjacent nanoparticles but reduces the film porosity and consequently the optical transparency. Currently the calcination technique is the only one that significantly improves the film adhesion and cohesion, but suggestions are offered to potentially improve the performance of films made by the other two methods. An alternative way to functionalize polycarbonate substrates for silica nanoparticle ISAM deposition is also presented. The molecular structure of polycarbonate at the surface can be modified by exposing it to deep UV (λ = 185, 254 nm). By doing so, the surface becomes populated with carboxylate species, and thus permits ISAM deposition of poly(allylamine hydrochloride) (PAH) and silica nanoparticles. A variety of spectroscopic methods show that the molecular structure is changed by this procedure, and SEM shows that UV treatment improves the uniformity of ISAM films on polycarbonate. Finally, PAH/silica nanoparticle ISAM films are deposited onto glass fibers. The fibers are used for mechanical reinforcement of polymer composite optical media. The role of the nanoparticle film on the fibers is to reduce light scattering at the interfaces of materials with different thermo-optic coefficients, in other words, transmittance losses associated with changes in temperature. Fiber bundles coated with silica nanoparticles suffer from unacceptable levels of aggregation, and hence do not currently improve the transmittance over the temperature spectrum. Some evidence is presented, however, to suggest that the transparency can be improved if fiber aggregation during ISAM deposition can be avoided.
- Impulse electrical breakdown of high-purity waterGehman, Victor H. (Virginia Tech, 1995-05-05)Experiments have been conducted on the electrical breakdown of high-purity water and water mixtures. The electrical regime of interest has been carefully defined and documented to consist of electrical impulses with approximately microsecond rise time and fall time greater than 65 microseconds, on approximately 81-square-centimeter-area planar electrodes with a dielectric gap of approximately one centimeter. The results of over 25,000 shots by a Marx generator have been distilled into database form in an Excel spreadsheet and analysis performed to try to find patterns or indirect evidence into the nature of the breakdown-initiation process. An extensive review of all the experiments, which had been conducted over eight years by the Naval Surface Warfare Center and which had been designed to find the largest water-breakdown fields, was conducted with the intention of delineating the physical factors that led to breakdown. A variety of theoretical models of breakdown initiation were compared to the data, until it became clear that many of the breakdowns were dominated by impurities of various sorts. An extensive study of old and new experiments led to a more detailed understanding of the phenomenology of impurity-dominated water breakdown (such as the process of "conditioning" the electrodes and hysteresis) and the proposal of a number of new experiments to further characterize the intrinsic role of electrode materials on determining high-electric-field dielectric breakdown in water.
- The influence of void space on antireflection coatings of silica nanoparticle self-assembled filmsYancey, S. E.; Zhong, W.; Heflin, James R.; Ritter, Alfred L. (American Institute of Physics, 2006-02-01)This study investigates the deposition by ionic self-assembly of alternating silica nanoparticle and poly(allyamine hydrochloride) layers with the goal to create a single-material antireflection coating. The condition that the optical thickness of the film be equal to lambda/4 can be satisfied by depositing the requisite number of bilayers to obtain minimum reflectivity at the chosen wavelength. The second condition for antireflection, that the index of refraction of the film be equal to n(c)=root n(1)n(2), where n(1) and n(2) are the refractive indices of the media on each side of the film, requires that n(c)=1.22 for a film with air on one surface and glass (assuming n=1.50) on the other. Such a low index of refraction can be created in films consisting of nanoparticles if the proper volume fraction of void space exists in the film. In the wavelength range lambda=350-700 nm, minimum reflectivities of >= 2.0%, <= 0.2%, and <= 0.2% were obtained with films created on both sides of a glass slide using 15, 45, and 85 nm average diameter silica nanoparticles, respectively. The maximum transmittances for the corresponding films were 97%, >= 98%, and >= 97%. The minimum reflectance of films prepared with 15 nm average diameter silica nanoparticles was limited by insufficient void volume in the films. The maximum transmittances of films prepared with 45 and 85 nm average diameter silica nanoparticles were limited by diffuse scattering arising from the inhomogeneous morphology of the films. The extinction of normal incident light (=1-R-T, where R and T are the reflectance and transmittance, respectively) provides a measure of diffuse scattering for light with wavelength longer than the absorption edge of the film. It was found that the extinction is proportional to 1/lambda(4) for lambda > 450 nm suggesting that the mechanism for extinction at long wavelengths is Rayleigh scattering. The Rayleigh slope (diffuse scattering intensity versus 1/lambda(4)) increased with increasing diameter silica nanoparticles. For a given average diameter silica nanoparticle, the Rayleigh slope increased with increasing film thickness for films less than approximately 150 nm thick, but did not depend on film thickness, within experimental scatter, for films that were thicker than 150 nm. The results suggest that the source of Rayleigh scattering was not in the bulk of the film (such as, fluctuations in the index of refraction), but rather was primarily associated with surface roughness. (c) 2006 American Institute of Physics.
- Measurement of the spectral momentum distribution of valence-electrons in amorphous-carbon by (e, 2e) spectroscopyKheifets, A. S.; Lower, J.; Nygaard, K. J.; Utteridge, S.; Vos, M.; Weigold, E.; Ritter, Alfred L. (American Physical Society, 1994-01-15)The spectral momentum density of the valence band of are evaporated amorphous carbon has been measured by (e, 2e) spectroscopy with significantly improved energy resolution relative to earlier studies. The valence band has been studied over a range of momenta from 0 to 1.6 a.u. with a resolution of 0.15 a.u. and over a range of binding energies from 9 eV above to 35 eV below the Fermi energy with a resolution of 1.5 eV. As seen in earlier studies, two major peaks are observed in the spectral momentum density which previously have been associated with sigma and pi bands in graphite. A third feature in the spectra, a weak shoulder approximately 4 eV below the Fermi energy, is observed. A heuristic model is introduced based on the assumption that the spectral momentum density of evaporated amorphous carbon is an angular average of the spectral momentum density of graphite. The behavior of the strongest feature in the experimental spectra is described well by this model, but the other two features, which are in the energy range of the graphitic pi, sigma(2), and sigma(3) bands, are poorly represented by the model. It is suggested that the poor agreement is due to rehybridization of these graphitic bands.
- Monte Carlo analysis of non-equilibrium steady states and relaxation kinetics in driven lattice gasesDaquila, George Lawrence (Virginia Tech, 2011-08-10)We numerically investigate the long-time behavior of the density-density auto-correlation function in driven lattice gases, with particle exclusion and periodic boundary conditions in one, two, and three dimensions using precise Monte Carlo simulations of larger system sizes than previous studies. In the one-dimensional asymmetric exclusion process on a ring with half the lattice sites occupied, we find that correlations induce extremely slow relaxation to the asymptotic power law decay We compare the crossover functions obtained from our simulations with various analytic results in the literature, and analyze the characteristic oscillations that occur in finite systems away from half-filling. As expected, correlations are weak in three dimensions and consequently the mean-field description is adequate. We also investigate the relaxation towards the non-equilibrium steady state in the two-time density-density auto-correlations, starting from strongly correlated initial conditions. We obtain simple aging scaling behavior in one, two, and three dimensions, with the expected power laws. We numerically investigate the behavior of driven lattice gases with nearest neighbor interactions at half-filling with periodic boundary conditions below and at the critical temperature using Monte Carlo simulations of very large lattices in two dimensions. This work is one of few that explores the relaxation to a non-equilibrium steady state. We obtain data collapse for the finite-size scaling form of density-density auto-correlation function at the critical point. We achieve data collapse using finite-size scaling of the time-dependent order parameter during the transient regime starting from strongly correlated initial conditions. We present simple aging scaling of the density-density auto-correlation function at the critical point starting from strongly correlated initial conditions using Monte Carlo simulations of two different lattice anisotropies. We thus unambiguously confirm the critical exponents determined by renormalization group methods using measurement of dynamic quantities in the transient regime. Measuring these dynamic quantities in the transient regime provides more conclusive measurements of the critical exponents than previous studies measuring static quantities in the stationary state. We provide qualitative arguments that the lattice anisotropy determines the steady-state for sub-critical quenches.
- Nanoscience Meets Geochemistry: Size-Dependent Reactivity of HematiteMadden, Andrew Stephen (Virginia Tech, 2005-06-02)Recent studies have demonstrated that nanoscale crystalline iron oxide minerals are common in natural systems. The discipline of nanoscience suggests that these particles in the size range of approximately 1-50 nm will have properties that deviate from the bulk properties of the same material and that these properties will change as a function of particle size. This study begins to fill the void of corresponding experimental investigations that apply the principles of nanoscience to the geochemical reactivity of nanominerals. The rate of Mn²⁺(aq) oxidation on hematite with average diameters of 7.3 nm and 37 nm was measured in the presence of O₂(aq). In the pH range of 7-8, the surface area normalized rate was one to two orders of magnitude greater on the 7.3 nm average diameter particles. Based on the application of electron transfer theory, it is hypothesized that the particles with diameters less than approximately 10 nm have surface crystal chemical environments which distort the symmetry of the MnMn²⁺ surface complex, reducing the energy required to reorganize the coordinated ligands after oxidation to Mn³⁺. Cu²⁺, an analog for Mn³⁺, was used to probe for the presence and nature of the proposed changes in surface structure. Cu²⁺ and Mn³⁺ show similar electronic structure changes in response to the surrounding crystal field due to their d-electron configurations and Jahn-Teller coordinative distortions. Batch sorption experiments on hematite nanoparticles revealed a shift in the pH-dependent adsorption of Cu²⁺(aq). Specifically, an affinity sequence of 7 nm > 25 nm = 88 nm was determined based on the shift of the 7 nm sorption edge to approximately 0.8 pH units lower than that for the 25 nm and 88 nm samples. These data support the hypothesis that unique binding sites exist on the 7 nm nanoparticles that are not significantly present on the larger particles. The National Nanotechnology Initiative stresses the need to address the broader societal impacts of nanoscale research. This dissertation embraces this viewpoint through the development and inclusion of "Nano2Earth: Introducing Nanotechnology Through Investigations of Groundwater," a curriculum which combines nanoscience with the Earth sciences for high school students.
- Non-Equilibrium Disordering Processes In binary Systems Due to an Active AgentTriampo, Wannapong (Virginia Tech, 2001-04-10)In this thesis, we study the kinetic disordering of systems interacting with an agent or a walker. Our studies divide naturally into two classes: for the first, the dynamics of the walker conserves the total magnetization of the system, for the second, it does not. These distinct dynamics are investigated in part I and II respectively. In part I, we investigate the disordering of an initially phase-segregated binary alloy due to a highly mobile vacancy which exchanges with the alloy atoms. This dynamics clearly conserves the total magnetization. We distinguish three versions of dynamic rules for the vacancy motion, namely a pure random walk , an "active" and a biased walk. For the random walk case, we review and reproduce earlier work by Z. Toroczkai et. al., [9] which will serve as our base-line. To test the robustness of these findings and to make our model more accessible to experimental studies, we investigated the effects of finite temperatures ("active walks") as well as external fields (biased walks). To monitor the disordering process, we define a suitable disorder parameter, namely the number of broken bonds, which we study as a function of time, system size and vacancy number. Using Monte Carlo simulations and a coarse-grained field theory, we observe that the disordering process exhibits three well separated temporal regimes. We show that the later stages exhibit dynamic scaling, characterized by a set of exponents and scaling functions. For the random and the biased case, these exponents and scaling functions are computed analytically in excellent agreement with the simulation results. The exponents are remarkably universal. We conclude this part with some comments on the early stage, the interfacial roughness and other related features. In part II, we introduce a model of binary data corruption induced by a Brownian agent or random walker. Here, the magnetization is not conserved, being related to the density of corrupted bits ρ. Using both continuum theory and computer simulations, we study the average density of corrupted bits, and the associated density-density correlation function, as well as several other related quantities. In the second half, we extend our investigations in three main directions which allow us to make closer contact with real binary systems. These are i) a detailed analysis of two dimensions, ii) the case of competing agents, and iii) the cases of asymmetric and quenched random couplings. Our analytic results are in good agreement with simulation results. The remarkable finding of this study is the robustness of the phenomenological model which provides us with the tool, continuum theory, to understand the nature of such a simple model.
- Nonlinear optical studies of dye-doped nematic liquid crystalsKlysubun, Prapong (Virginia Tech, 2002-03-28)Nematic liquid crystals possess large optical nonlinearities owing to their large refractive index anisotropy coupled with the collective molecular reorientation. Doping absorbing dyes into liquid crystals increases their optical responses significantly due to increased absorption in the visible region, absorption-induced intermolecular torque, cis-trans photoisomerization, and other guest-host effects. The guest-host mixtures can be employed in display applications, optical storage devices, and others. In this dissertation, nonlinear optical studies were carried out on dye-doped nematic liquid crystal cells. The main objectives of the studies were to distinguish and characterize the several processes that can lead to the formation of dynamic gratings of different types in the samples, and to study the photorefractive and the orientational responses of these samples. Furthermore, we tried to explain and model the dynamical behaviors of the observed grating formations. The experimental techniques employed in this study include asymmetric two-beam coupling, forced light scattering, and polarization holographic method. The asymmetric two-beam coupling experiments revealed that the induced grating was a photorefractive phase grating created by the nematic director reorientation within the plane of incidence. The dynamics of the beam coupling showed that two different mechanisms with different temporal responses were involved. The grating translation technique identified both gratings as pure photorefractive index gratings with phase shifts of ~ p/2 between the grating and the interference pattern. In addition, the dynamical behavior of the grating formation, obtained from forced light scattering experiments, also exhibited a two-time constant response. The dynamical behaviors of the build-up and decay of the photocurrent were investigated. The two dynamics exhibited both a two-time constant behavior, suggesting that the origin of the two-time constant dynamics observed in the two-beam coupling and the forced light scattering experiments resides in the process of photo-charge generation. The photorefractive gain coefficients were found to be in the range of 100 – 400 cm-1. The values of the nonlinear optical Kerr index (~ 0.08 cm2/W) measured in samples with certain dye/liquid crystal combinations are higher than what has been observed in other dye-doped nematics and other liquid crystal/polymer systems. All the samples showed a threshold behavior with respect to the magnitude of the applied electric field. This threshold behavior was observed both in forced light scattering experiments and polarization holographic experiments. We believe that the origin of this threshold lies in the process of photogeneration, which was found to exhibit the same threshold behavior at the same value of the applied voltage. An asymmetry of the photorefractive gain with respect to the direction of the applied electric field was observed in samples with high dye concentration. This was attributed to the beam fanning effect, which has also been observed in other high-gain photorefractive materials. Polarization holographic measurements showed that the dye enhancement effect is primarily due to the intermolecular interaction between the dye molecules and the liquid crystal host, and that the trans-cis photoisomerization plays a lesser role. The photoinduced orientational response was also studied using polarization holographic experiments. A number of observations confirmed that the birefringent grating is due to the nematic director reorientation within the plane of incidence, under the combined effect of the applied electric field and the optical field. The diffraction efficiency was found to depend linearly on the writing beam power, while the dependence of the self-diffraction efficiency on the writing beam power roughly assumes a cubic relationship. The dynamical behavior of the birefringent grating formation was investigated. The build-up dynamics was found to be best modeled as a double-time constant response, while the decay is best fitted by a single exponential. The response of the samples to an oscillating electric field was studied as a function of the modulation frequency. Very interesting and reproducible dynamics was observed, revealing the complex dynamical response of the liquid crystal director to the magnitude and rate of change of an applied electric field. The small signal response was also measured, but did not reveal any sign of a resonance behavior. The conductivity and the photoconductivity of the samples were measured. The relationship between the measured current and the applied voltage was found to be cubic at low applied voltage, and to become linear at higher applied voltage. We could explain this behavior using a double-charge-injection-in-a-weak-electrolyte model, but this is only one of the possible mechanisms that could explain this behavior. The photocurrent was found to increase linearly with the illumination power, which indicates that the charge carrier recombination rate is proportional to the carrier density. The measured electrical conductivity was found to be proportional to the square root of the dye concentration, confirming the validity of the proposed charge-injection model.
- Optical excitations in Bi2Sr2CuO6 and Bi2Sr2CaCu2O8: Evidence for localized (excitonic) and delocalized charge-transfer gapsWang, Y. Y.; Ritter, Alfred L. (American Physical Society, 1991-01)The optical properties of Bi2Sr2CuO6 (2:2:0:1) and Bi2Sr2CaCu2O8 (2:2:1:2) have been investigated by transmission electron-energy-loss spectroscopy. At low energy, E(loss) less-than-or-equal-to 10.0 eV, common features are observed in the spectra of these two materials at E(loss) = 0.0, approximately 2.7, 3.6, and 4.6 eV. The effective number of charges associated with these excitations has been estimated using the optical sum rule, and from the ratio of effective charges in the two materials, the origin of this feature has been inferred based on the relative number of Cu-O2 and Bi-O layers per formula unit. The effective-charge ratio for the free carriers at zero energy loss, N2:2:1:2/N2:2:0:1 = 5.0, could not be used to determine whether the carriers were in the Cu-O2 or Bi-O planes because the oxygen doping in the two materials was not known. But at E(loss) = 2.7 and 3.6 eV, the effective-charge ratio is 2.6 indicating that these transitions are associated with the Cu-O2 planes since the ratio is close to 2/1. The effective-charge ratio is 0.9 for E(loss) = 4.6 eV suggesting that this excitation is localized in the Bi-O planes. If the two excitations in the Cu-O2 layers of 2:2:0:1 and 2:2:1:2 are identified with the delocalized and localized charge-transfer reactions [Mark S. Hybertsen, Michael Schluter, and Niels E. Christensen, Phys. Rev. B 39, 9028 (1989)], then the three-band Hubbard parameters E = E(p) - E(d) and U(pd) (E is the energy difference between the Cu 3d and O 2p levels and U(pd) is the Coulomb repulsion between two holes occupying adjacent Cu and O sites) are 1.8 and 0.9 eV, respectively, with an uncertainty of +/- 0.5 eV.
- Optical Limiting and Degenerate Four-Wave Mixing in Novel FullerenesMarciu, Daniela (Virginia Tech, 1999-02-09)Two experimental methods, optical limiting and degenerate four-wave mixing, are employed to study the nonlinear optical properties of various novel fullerenes structures. Optical limiting refers to decreased transmittance of a material with increased incident light intensity. Detailed measurements of the wavelength-dependence of fullerene optical limiters have illustrated several key features of reverse saturable absorption. Most important among these is the requirement of weak but non-negligible ground state absorption. We have shown that the optical limiting performance of C₆₀ can be extended into the near infrared range by appropriate modifications of the structure such as higher cage fullerenes or derivatization of the basic C₆₀ molecule. The higher cage fullerene C₇₆ shows improved optical limiting behavior compared to C₆₀, for wavelengths higher than 650 nm, but becomes a weak limiter in the 800 nm range. C₈₄, even at high concentrations in [alpha]-chloronaphthalene, does not reach the good performance of C₆₀, but instead shows weak optical limiting in the 800 nm range. We also demonstrate that by attaching various groups to the C₆₀ molecule, we can extend the optical limiting performance in the near infrared regime. The C₆₀ derivatives studied, (C₆₀ cyclic ketone, C₆₀ secondary amine, C₆₀CHC₆H₄CO₂H, and C₆₀C₄H₄(CH₃)CH₂O₂C(CH₂)CO₂H), have a similar characteristic: the attached groups cause a symmetry-breaking of the C₆₀ sphere and, therefore, there are new allowed transitions that appear as absorption features up to 750 nm. The optical limiting measurements show that these materials, even for low input energies, have an exceptionally strong optical limiting response in the 640 to 750 nm spectral region. For wavelengths higher than 800 nm, however, they become transparent and no optical limiting is observed. Excited state absorption cross-sections obtained from analysis of the optical limiting data reveal that the C₆₀ derivatives have a maximum triplet-triplet absorption cross-section at 700 nm, which is shifted from the 750 nm value for the C₆₀ molecule. For the first time, optical limiting measurements are performed on five separate C₈₄ isomers. These intriguing results show that the optical limiting behavior is strongly dependent on the cage symmetry. It is also found that the most abundant isomer does not have the strongest optical limiting performance, but is in fact one of the weaker optical limiters of the isomers isolated so far. The endohedral metallofullerenes are a unique class of fullerene materials and consist of one or more metal atoms encapsulated inside the buckyball cage. An important characteristic of these materials is the charge-transfer from the dopant atoms to the fullerene cage, which has a high electron affinity. The charge-transfer is similar to the optical excitation in a material, but although the electrons are placed in the lowest unoccupied molecular orbital (LUMO), there are no holes produced in the highest occupied molecular orbital (HOMO). This is an important analogy, since it has been previously shown that optical excitation enhances the nonlinear optical properties of a material. The nonresonant degenerate four-wave mixing experiments performed on the endohedral metallofullerene Er₂@C₈₂, at 1064 nm, show that the third order nonlinear susceptibility value is increased by orders of magnitude relative to the empty cage fullerenes, thus, confirming the charge-transfer process from the encapsulated atoms to the fullerene cage. We obtain a value [gamma]xyyx(3)( [omega]; [omega], [omega], [omega])= 8.65 × 10⁻³² esu for the molecular second order hyperpolarizability, which is almost three orders of magnitude larger than the values reported in literature for an empty cage fullerene.
- Optical studies of GaAs:C grown at low temperature and of localized vibrations in normal GaAs:CVijarnwannaluk, Sathon (Virginia Tech, 2002-04-25)Optical studies of heavily-doped GaAs:C grown at low temperature by molecular beam epitaxy were performed using room-temperature photoluminescence, infrared transmission, and Raman scattering measurements. The photoluminescence experiments show that in LT-GaAs:C films grown at temperatures below 400 °C, nonradiative recombination processes dominate and photoluminescence is quenched. When the growth temperature exceeds 400 °C, band-to-band photoluminescence emission appears. We conclude that the films change in character from LT-GaAs:C to normal GaAs:C once the growth temperature reaches 400 °C. Annealing, however, shows a different behavior. Once grown as LT-GaAs:C, this material retains its nonconducting nonluminescing LT characteristics even when annealed at 600 °C. The Raman-scattering measurements showed that the growth temperature and the doping concentration influence the position, broadening, and asymmetry of the longitudinal-optical phonon Raman line. We attribute these effects to changes in the concentration of interstitial carbon in the films. Also, the shift of the Raman line was used to estimate the concentration of arsenic-antisite defects in undoped LT-GaAs. The infrared transmission measurements on the carbon-doped material showed that only a fraction of the carbon atoms occupy arsenic sites, that this fraction increases as the growth temperature increases, and that it reaches about 100% once the growth temperature reaches 400 °C. The details of all these measurements are discussed. Infrared transmission and photoluminescence measurements were also carried out on heavily-doped GaAs:C films grown by molecular beam epitaxy at the standard 600 C temperature. The infrared results reveal, for dopings under 5 x 10⁹ cm⁻³, a linear relation between doping concentration and the integrated optical absorption of the carbon localized-vibrational-mode band. At higher dopings, the LVM integrated absorption saturates. Formation of CAs-CAs clusters is proposed as the mechanism of the saturation. The photoluminescence spectra were successfully analyzed with a simple model assuming thermalization of photoelectrons to the bottom of the conduction band and indirect-transition recombination with holes populating the degenerately doped valence band. The analysis yields the bandgap reduction and the Fermi-level-depth increase at high doping.