Thesis (Ph. D.)--Duke University, 2008. / Includes bibliographical references.

Thesis (doctoral)--Ludwig-Maximilians-Universität München, 2003. / Accompanying CD-ROM includes color images of all figures. Includes bibliographical references (p. 130-135). Original thesis in German available online via the Internet.

Thesis (Ph. D. in Physics)--Vanderbilt University, May 2006. / Title from title screen. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 246-276).

Orientador: Alessandra Nara de Souza Rastelli / Resumo: Estudos recentes relatam que resinas compostas contendo nanopartículas (NPs) de óxidos metálicos, tais como óxido de zinco (ZnO) e dióxido de titânio (TiO2) têm potencial antibacteriano e podem controlar a formação do biofilme oral cariogênico. O objetivo desse estudo foi avaliar a capacidade antibacteriana de uma resina composta modificada por NPs de óxido de zinco e dióxido de titânio puras e decoradas com prata (ZnO, ZnO/Ag, TiO2 e TiO2/Ag), bem como, avaliar as propriedades de resistência à compressão e à tensão diametral, estabilidade de cor, rugosidade superficial e grau de conversão após modificação da resina composta com as NPs. As NPs foram sintetizadas pelos métodos dos precursores poliméricos e hidrotermal assistido por micro-ondas, e caracterizadas por DRX, área de superfície BET, FTIR e MET. A resina FiltekTM Z350XT modificada com 0,5; 1 e 2% (em massa) foi testada sobre Streptococcus mutans por meio do teste do contato direto (UFC/mL) para determinação da menor concentração inibitória e então avaliada em biofilme de 7 dias por meio decontagem das unidades formadoras de colônias (UFC/mL). As resistências à compressão e à tração diametral da resina composta modificada (n=40) foram avaliadas utilizando-se máquina de ensaio universal (EMIC). O grau de conversão (n=25) foi realizado por análise em FTIR e a leitura da rugosidade superficial (n=50) foi realizada utilizando-se rugosímetro portátil. A estabilidade de cor (n=180) foi avaliada por leitura espectrofotométri... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Different methods to inhibit biofilm formation on dental restorative materials have been studied for decades and recent studies report that composite resins containing metal oxide nanoparticles (NPs), such as zinc oxide (ZnO) and titanium dioxide (TiO2), have antibacterial potential and can control the formation of cariogenic oral biofilm. In this way, the purpose of this study was to evaluate the antibacterial capacity of a resin modified by pure and silver decorated ZnO and TiO2 (ZnO, ZnO/Ag, TiO2 and TiO2/Ag) NPs and to evaluate the compressive and diametral tensile strength, color stability, surface roughness and degree of conversion after modification of the composite resin with the NPs. The NPs were synthesized by polymeric precursor and microwave-assisted hydrothermal methods, characterized by XRD, BET surface area, FTIR and MET. The direct contact test with Filtek ™ Z350XT modified with 0.5; 1 and 2% (by mass) of NPs against Streptococcus mutans was performed in order to choose the minor concentration to perform the other tests. The modified resin was tested against the 7- days S. mutans biofilm. The compressive strength and diametral tensile strength of the modified composite resin (n = 40) was tested using a universal test machine (EMIC). The degree of conversion (n = 25) was performed by FTIR analysis and the surface roughness reading (n = 50) was performed using a portable surface roughness tester. The color stability (n=180) was evaluated by spectrophotometric readings after storage in coffee solution and artificial saliva. The data was analyzed using the software IBM SPSS Statistics 20.0 (SPSS Inc. Chicago, USA). One-way ANOVA were performed to antibacterial and mechanical tests data, two-way ANOVA for degree of conversion and a mixed model repeated measurements ANOVA and a post hoc test for repeated measures with adjustment... (Complete abstract electronic access below) / Doutor

abstract: The research of this dissertation has involved the nanoscale quantitative characterization of patterned magnetic nanostructures and devices using off-axis electron holography and Lorentz microscopy. The investigation focused on different materials of interest, including monolayer Co nanorings, multilayer Co/Cu/Py (Permalloy, Ni81Fe19) spin-valve nanorings, and notched Py nanowires, which were fabricated via a standard electron-beam lithography (EBL) and lift-off process. Magnetization configurations and reversal processes of Co nanorings, with and without slots, were observed. Vortex-controlled switching behavior with stepped hysteresis loops was identified, with clearly defined onion states, vortex states, flux-closure (FC) states, and Omega states. Two distinct switching mechanisms for the slotted nanorings, depending on applied field directions relative to the slot orientations, were attributed to the vortex chirality and shape anisotropy. Micromagnetic simulations were in good agreement with electron holography observations of the Co nanorings, also confirming the switching field of 700-800 Oe. Co/Cu/Py spin-valve slotted nanorings exhibited different remanent states and switching behavior as a function of the different directions of the applied field relative to the slots. At remanent state, the magnetizations of Co and Py layers were preferentially aligned in antiparallel coupled configuration, with predominant configurations in FC or onion states. Two-step and three-step hysteresis loops were quantitatively determined for nanorings with slots perpendicular, or parallel to the applied field direction, respectively, due to the intrinsic coercivity difference and interlayer magnetic coupling between Co and Py layers. The field to reverse both layers was on the order of ~800 Oe. Domain-wall (DW) motion within Py nanowires (NWs) driven by an in situ magnetic field was visualized and quantified. Different aspects of DW behavior, including nucleation, injection, pinning, depinning, relaxation, and annihilation, occurred depending on applied field strength. A unique asymmetrical DW pinning behavior was recognized, depending on DW chirality relative to the sense of rotation around the notch. The transverse DWs relaxed into vortex DWs, followed by annihilation in a reversed field, which was in agreement with micromagnetic simulations. Overall, the success of these studies demonstrated the capability of off-axis electron holography to provide valuable insights for understanding magnetic behavior on the nanoscale. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2010

abstract: The research of this dissertation involved quantitative characterization of electrostatic potential and charge distribution of semiconductor nanostructures using off-axis electron holography, as well as other electron microscopy techniques. The investigated nanostructures included Ge quantum dots, Ge/Si core/shell nanowires, and polytype heterostructures in ZnSe nanobelts. Hole densities were calculated for the first two systems, and the spontaneous polarization for wurtzite ZnSe was determined. Epitaxial Ge quantum dots (QDs) embedded in boron-doped silicon were studied. Reconstructed phase images showed extra phase shifts near the base of the QDs, which was attributed to hole accumulation in these regions. The resulting charge density was (0.03±0.003) holes/nm3, which corresponded to about 30 holes localized to a pyramidal, 25-nm-wide Ge QD. This value was in reasonable agreement with the average number of holes confined to each Ge dot determined using a capacitance-voltage measurement. Hole accumulation in Ge/Si core/shell nanowires was observed and quantified using off-axis electron holography and other electron microscopy techniques. High-angle annular-dark-field scanning transmission electron microscopy images and electron holograms were obtained from specific nanowires. The intensities of the former were utilized to calculate the projected thicknesses for both the Ge core and the Si shell. The excess phase shifts measured by electron holography across the nanowires indicated the presence of holes inside the Ge cores. The hole density in the core regions was calculated to be (0.4±0.2) /nm3 based on a simplified coaxial cylindrical model. Homogeneous zincblende/wurtzite heterostructure junctions in ZnSe nanobelts were studied. The observed electrostatic fields and charge accumulation were attributed to spontaneous polarization present in the wurtzite regions since the contributions from piezoelectric polarization were shown to be insignificant based on geometric phase analysis. The spontaneous polarization for the wurtzite ZnSe was calculated to be psp = -(0.0029±0.00013) C/m2, whereas a first principles' calculation gave psp = -0.0063 C/m2. The atomic arrangements and polarity continuity at the zincblende/wurtzite interface were determined through aberration-corrected high-angle annular-dark-field imaging, which revealed no polarity reversal across the interface. Overall, the successful outcomes of these studies confirmed the capability of off-axis electron holography to provide quantitative electrostatic information for nanostructured materials. / Dissertation/Thesis / Ph.D. Physics 2011

abstract: As existing solar cell technologies come closer to their theoretical efficiency, new concepts that overcome the Shockley-Queisser limit and exceed 50% efficiency need to be explored. New materials systems are often investigated to achieve this, but the use of existing solar cell materials in advanced concept approaches is compelling for multiple theoretical and practical reasons. In order to include advanced concept approaches into existing materials, nanostructures are used as they alter the physical properties of these materials. To explore advanced nanostructured concepts with existing materials such as III-V alloys, silicon and/or silicon/germanium and associated alloys, fundamental aspects of using these materials in advanced concept nanostructured solar cells must be understood. Chief among these is the determination and predication of optimum electronic band structures, including effects such as strain on the band structure, and the material's opto-electronic properties. Nanostructures have a large impact on band structure and electronic properties through quantum confinement. An additional large effect is the change in band structure due to elastic strain caused by lattice mismatch between the barrier and nanostructured (usually self-assembled QDs) materials. To develop a material model for advanced concept solar cells, the band structure is calculated for single as well as vertical array of quantum dots with the realistic effects such as strain, associated with the epitaxial growth of these materials. The results show significant effect of strain in band structure. More importantly, the band diagram of a vertical array of QDs with different spacer layer thickness show significant change in band offsets, especially for heavy and light hole valence bands when the spacer layer thickness is reduced. These results, ultimately, have significance to develop a material model for advance concept solar cells that use the QD nanostructures as absorbing medium. The band structure calculations serve as the basis for multiple other calculations. Chief among these is that the model allows the design of a practical QD advanced concept solar cell, which meets key design criteria such as a negligible valence band offset between the QD/barrier materials and close to optimum band gaps, resulting in the predication of optimum material combinations. / Dissertation/Thesis / Ph.D. Electrical Engineering 2011

Les oxydes simple ou double de métaux de transition (OMTs) sont des matériaux prometteurs pour les applications en tant qu’électrode dans des pseudo supercondensateurs ou des supercondensateur redox car ils peuvent présenter un gain de densité d’énergie résultant des réactions redox.Ce mémoire de thèse a pour but l’étude et l’optimisation du comportement électrochimique d’électrodes d’ oxydes simple de manganèse ainsi que le développement de nouvelles électrodes à base d’oxydes doubles (OMTs) conçues pour le stockage d’énergie dans les supercondensateurs redox , grâce au dépôt de ces matériaux actifs sur un collecteur de courant en acier inoxydable par électrodéposition ce qui représente une technique flexible et peu couteuse.Afin d’étudier ces électrodes, leurs propriétés physico-chemique ont été caractérisées par microscopie électronique (SEM/TEM), spectroscopie X à dispersion d’énergie (EDX), par diffraction X (XRD), par spectroscopies Raman & Infrarrougee (FTIR), par microsopie à force atomique (AFM) et par magnétométrie SQUID (superconducting quantum interference device). Leurs propriétés electrochimique ont été caractérisées par voltamperométrie cyclique et chronopotentiométrie.Les résultats détaillent la croissance et les caractérisations physico-chimique et électrochimique de plusieurs oxydes TMOS (TM=Mn, Mn-Co, Ni-Mn) ainsi que d’hydroxydes de Ni-Co préparés par électrodéposition. Le contrôle de la morphologie et de l’architecture des électrodes, en vue de créer des surfaces ayant des grandes surfaces actives, est le paramètre clé pour augmenter la performance du pseudo-condensateur. Dans le détail, le travail de recherche a contribué au développement de nouveau matériaux pour des électrodes à base d’oxyde (et hydroxydes) pour les supercondensateurs redox par: (i) la mise en œuvre de nouvelles électrodes avec des bonnes performances pseudocapacitive pour des supercondesateurs (Mn oxydes, Ni-Mn oxydes, Ni-Co hydroxydes), (ii) la pleine compréhension de l’effet du recuit sur la transformation de l’hydroxyde préparés par électrodéposition en oxyde et de la corrélation résultante avec les propriétés électrochimiques pour des électrodes à base d’oxyde Mn-Co, (iii) la description détaillée du mécanisme de croissance de films d’ oxyde de Mn préparés par électrodéposition à partir d’électrolytes à base de nitrates, (iv) la mise en évidence d’une méthode prometteuse de mise en forme et contrôle de la morphologie de surface d’oxydes mixtes préparés par électrodéposition et ce à travers le contrôle de la croissance d’oxyde simples , (v) la compréhension du mécanisme de nucléation des hydroxydes préparés par électrodéposition (Ni-Co hydroxydes). Les résultats de ce mémoire de thèse vont au delà de l’état de l’art et apportent des faits marquants pour l’avancée du développement de nouveaux matériaux pour électrodes dans des supercondensateurs redox. / Transition metal oxides (TMOs) and double TMOs are promising materials for application as electrodes in pseudo supercapacitors or redox supercapacitors because they can exhibit increased energy density resulted from redox reactions.This PhD dissertation aims at studying and improving the electrochemical behavior of single TMOs - manganese oxides and at developing new double TMOs electrodes tailored for energy storage in redox supercapacitors, by depositing the active materials directly on stainless steel current collector via a flexible and costless electrodeposition route.To study these electrodes for supercapacitors, their physic-chemical properties were characterized by scanning/transmission electron microscopy (SEM/TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman & Infrared spectroscopy (FTIR), atomic force microscopy (AFM) and superconducting quantum interference device (SQUID). Their electrochemical properties were characterized by cyclic voltammetry and chronopotentiometry.The results have detailed the growing, physic-chemical and electrochemical characterizations of Mn oxides, Mn-Co oxides, Ni-Mn oxides and Ni-Co hydroxides prepared by electrodeposition. Tailoring the morphology and architecture these electrodes and creating surfaces exhibiting high surface area are key parameters for enhanced pseudocapacitive performance. In detail, the research work contributed to the development of novel oxide (and hydroxides) materials for redox supercapacitors by: (i) providing novel electrodes with good pseudocapacitive performance for supercapacitors (Mn oxides, Ni-Mn oxides, Ni-Co hydroxides), (ii) fully understanding the effect of annealing on the transformation from electrodeposited mixed hydroxides to mixed oxide and their correlation with electrochemical properties for the Mn-Co oxide – based electrodes, (iii) detailing the growing mechanisms of Mn oxide films electrodeposited from nitrate based electrolyte, (iv) revealing a promising way of tailoring surface morphology of electrodeposited mixed oxides by controlling the growth of single oxides, (v) understanding the nucleation mechanism of hydroxides prepared by electrodeposition (Ni-Co hydroxides).Thus, the results of this PhD dissertation go beyond the state-of-the-art and provided valuable highlights to advance the development of novel electrode materials for redox supercapacitors.

Surface plasmon is the quantized collective oscillation of the free electron gas in a metallic material. By coupling surface plasmons with photons in different nanostructures, researchers have found surface plasmon polaritons (SPP) and localized surface plasmon resonance (LSPR), which are widely adopted in biosensing, single molecule sensing and detection via surface enhanced raman scattering (SERS), photothermal ablation treatments for cancer, optical tagging and detection, strain sensing, metamaterials, and other applications. The overall objective of this dissertation is to investigate both how mechanics impacts the optical properties, and also how optics impacts the mechanical properties of metal nanostructures reversely. Mechanically engineering individual nanostructures(forward coupling) offers the freedom to alter the optical properties with more flexibility and tunability. It is shown that elastic strain can be applied to gold nanowires to reduce the intrinsic losses for subwavelength optical signal processing, leading to an increase of up to 70% in the surface plasmon polariton propagation lengths at resonance frequencies. Apart from strain engineering, defects are another important aspect of mechanically engineering nanoscale materials, whose impacts on the optical properties of metal nanostructures remain unresolved. An atomic electrodynamic model has been derived to demonstrate that those effects are crucial for ultrasmall nanoparticles with characteristic sizes around 2 nm, and can be safely ignored for those larger than about 5 nm due to the important contribution of nanoscale surface effects. Another key focus of this research project (reverse coupling) is to investigate the currently unknown effects that an external optical field has on the mechanical properties of metal nanostructures. Since each atom in the nanostructure acts as a dipole due to induced electron motions, this optical excitation introduces additional dipolar forces that add to the standard mechanical atomic interactions, which could alter the mechanical properties of the nanostructures. Furthermore, it is shown that when linking mechanics with LSPR, because the metal is dispersive, the mechanical behavior or the strength of the nanostructure should be dependent on the frequency of the electromagnetic excitation. To study this phenomenon, a simpler case with an electrostatic field excitation is considered first, and conclusions are reached on how static fields can be used to tune the elasticity of metallic nanostructures with different sizes and axial orientations and surfaces. Then building upon those understandings, studies were carried out in determining the effects of an optical field, specifically at LSPR frequency, on the mechanical properties of metallic nanostructures. It is found that the initial relaxation strain induced by the static field or optical field is the key factor leading to the variations in the stiffness of the metallic nanostructures that are excited by optical fields at the LSPR frequencies.