In this work columnar nanospirals of AlInN were grown on top of TiN-coated sapphire substrates by magnetron sputtering. A variety of samples with different growth parameters were fabricated and investigated. The main objectives in this work were to optimize the degree of circular polarization and to control the active wavelength region for where this polarization effect occurs. Attempts were made to achieve a high degree of circular polarization in both reflected and transmitted light. It is shown that for reflected light it is possible to achieve a high degree of circular polarization within the visible wavelength regions. For transmitted light the concept of achieving circularly polarized light is proven.

<p>Nanometer-scale metallic structures have been widely and intensively studied over the last decade because of their remarkable plasmonic properties that can enhance local electromagnetic (EM) fields. However, most plasmonic applications are restricted to the visible and near infrared photon energies due to the limitations of the surface plasmon resonance energies of the most commonly used plasmonic metals: Au and Ag. Plasmonic applications in ultraviolet (UV) are of great interest because Raman scattering sections are larger and do not overlap fluorescence spectra. UV plasmonics also benefit from high spatial resolution and low penetration depth. However, an appropriate UV plasmonic material must be identified.</p><p>We proposed and demonstrated that gallium is a highly-promising and compelling material for UV nanoplasmonics through synthesis of size-controlled nanoparticle arrays, EM modeling of local field enhancement, ellipsometric and spatial characterization of the arrays, and analytical measurement of UV- enhanced Raman and fluorescence spectra. Self-assembled arrays of hemispherical gallium nanoparticles deposited by molecular beam epitaxy on a sapphire support are characterized with spatial and ellipsometric measurements. Spin-casting a thin film of crystal violet upon these nanoparticles permitted the demonstration of surface-enhanced Raman spectra, fluorescence, and molecular photodegradation following excitation by a HeCd laser operating at 325 nm (UV). Measured local Raman enhancement factors exceeding 10<super>7</super> demonstrated the potential of gallium nanoparticle arrays for plasmonically-enhanced ultraviolet detection and remediation.</p> / Dissertation

Pastarąjį dešimtmetį, intensyviai vystantis nanotechnologijoms, ženkliai išaugo technologinių metodų, įgalinančių suformuoti darinius, kuriuose elementų dydžiai būtų tarp 1 ir 100 nm, paieška. Šiai specifinei nanostruktūrinių medžiagų grupei skiriamas ypatingas dėmesys dėl naujų fizikinių reiškinių ir ypač - praktinių taikymų, kuriuos atveria šie dariniai. Šiame darbe aptariamos elektrocheminės technologijos, skirtos kontroliuojamos morfologijos porėtojo silicio formavimui. Suformuoti hibridiniai por-Si dariniai su metalais. Sukurta biomolekulių įterpimo į porėtuosius silicio darinius technologija bei tirta biomolekulių sąveika su kietakūniais padėklais. Nagrinėjami GaP nanodarinių formavimo elektrocheminio ėsdinimo būdu dėsningumai bei jų taikymo galimybės dujų sensoriuose. Įsisavinta nanoporėtųjų dielektrinių terpių ir hibridinių nanodarinių formavimo technologija bei tirtos jų savybės. / Over the past decade, the intensive development of nanotechnology was made to increase significantly the number of methods to form the structures of a size between 1 and 100 nm. It should be emphasized that nanostructured materials are interesting both because of perspectives in practical applications and new physical phenomena. In this work the electrochemical technique for the control of morphology of porous silicon matrix developed. Hybrid por-Si structures with metals were made. The method for infiltration of biomolecules into the porous silicon structures was developed and the interaction between silicon and bio-molecules was investigated. GaP nanostructures were formed by electrochemical etching and the possibilities of their application for gas sensors were estimated. Nanoporous and Fe-doped silica films on Si were made and the developed structures were characterized by their structural, optical or magnetic properties.

Over the past decade, the intensive development of nanotechnology was made to increase significantly the number of methods to form the structures of a size between 1 and 100 nm. It should be emphasized that nanostructured materials are interesting both because of perspectives in practical applications and new physical phenomena. In this work the electrochemical technique for the control of morphology of porous silicon matrix developed. Hybrid por-Si structures with metals were made. The method for infiltration of biomolecules into the porous silicon structures was developed and the interaction between silicon and bio-molecules was investigated. GaP nanostructures were formed by electrochemical etching and the possibilities of their application for gas sensors were estimated. Nanoporous and Fe-doped silica films on Si were made and the developed structures were characterized by their structural, optical or magnetic properties. / Pastarąjį dešimtmetį, intensyviai vystantis nanotechnologijoms, ženkliai išaugo technologinių metodų, įgalinančių suformuoti darinius, kuriuose elementų dydžiai būtų tarp 1 ir 100 nm, paieška. Šiai specifinei nanostruktūrinių medžiagų grupei skiriamas ypatingas dėmesys dėl naujų fizikinių reiškinių ir ypač - praktinių taikymų, kuriuos atveria šie dariniai. Šiame darbe aptariamos elektrocheminės technologijos, skirtos kontroliuojamos morfologijos porėtojo silicio formavimui. Suformuoti hibridiniai por-Si dariniai su metalais. Sukurta biomolekulių įterpimo į porėtuosius silicio darinius technologija bei tirta biomolekulių sąveika su kietakūniais padėklais. Nagrinėjami GaP nanodarinių formavimo elektrocheminio ėsdinimo būdu dėsningumai bei jų taikymo galimybės dujų sensoriuose. Įsisavinta nanoporėtųjų dielektrinių terpių ir hibridinių nanodarinių formavimo technologija bei tirtos jų savybės.

Silicon based hydrogenated amorphous semiconducting (intrinsic and n/p doped a-Si:H and a-Si1-xCx:H) thin films have been deposited by plasma enhanced chemical vapor deposition (PECVD) system. In order to analyze the optical response of these amorphous films, intrinsic optical absorption mechanisms have resumed and spectral variations of absorption coefficient &amp / #61537 / (E) are derived. The exponential variation of absorption coefficient for energies below the band edge is discussed in the frame of randomly distributed square well like potential fluctuations of localized states. Urbach constant EU and the slope B are deduced as disorder parameters. Both intensity sensitive transmittance and reflectance, and amplitude/phase sensitive ellipsometric techniques for multilayer thin films are theoretically and practically treated. Various methodologies are developed for the determination of thickness, refractive index and absorption coefficient of the films. A reflectance unit is adapted to the spectrometer and all the measuring instruments are computerized and relevant software packets have been developed. IR spectroscopy has been used for determination of mainly hydrogen concentrations and bonding properties. Establishing the production-characterization-improved growth conditions cycle successfully, the following results are obtained: (a) determination of lateral inhomogeneity of films along the radial direction of the plasma reactor, (b) determination of vertical inhomogeneity due to both substrate and air ambient, (c) perfect adjustment of refractive index and band gap of a-Si1-xCx:H films by changing carbon content of the films, (d) effect of plasma power density on both growth and carbon content.

The fundamentals of the ellipsometry are reviewed in order to point out the strengths and weaknesses of the ellipsometric measurements. The effects of the surface conditions (such as degree of cleanliness, contaminated thin layer, roughness etc&hellip / ) on the ellipsometric variables are experimentally studied / the optimum procedures have been determined. Hydrogenated amorphous silicon carbide (a-Si1-xCx:H) thin films are produced by plasma enhanced chemical vapor deposition (PECVD) technique with a circular reactor, in a way that RF power and carbon contents are taken as variables. These samples are analyzed using multiple angle of incidence ellipsometer and uv-vis spectrometer. These measurements have inhomogeneities in optical constants, such as thicknesses, refractive indices and optical energy gaps along the radial direction of the reactor electrode for different power and carbon contents.

A reflection retarder is a device that induces a change in the phase between the parallel and perpendicular components, of the electric field, to the plane of incidence while maintaining the relative amplitudes. A film-substrate reflection retarder is a reflection retarder that only consists of a film-substrate system. Film-substrate reflection retarders have been previously studied in the negative, zero, and positive systems. The type of system is determined by the relationship between the refractive index of the ambient N0, film N1, and substrate N2: if N1<(N0*N2)^(1/2) , the system is negative; if N1=(N0*N2)^(1/2), the system is zero; if N1>(N0*N2)^(1/2), the system is positive. It has been determined that is the condition required to achieve reflection retarders, in general. Angle-of-incidence tunable (AIT) retarder designs have not been investigated for the zero system, but have been studied in the negative system. An exact retarder in the zero system only exists at a single angle of incidence and a corresponding single film thickness. By approximating the retarder condition to allow the relative amplitudes to be within 5% of the exact value of unity, it is possible to realize unique AIT retarders in the zero system: retarders that can be operated over a continuous range of angles of incidence resulting in a large range of phase shifts approaching 360°. It is possible to have multiple angles of incidence with a difference of between their respective phase shifts. By inducing a phase shift of, it is possible to modulate the polarization of light. By employing an approximation of the retarder condition, AIT retarder designs were developed. The design’s tolerance to changes in design parameters is analyzed and discussed.

Cette thèse porte sur les propriétés thermooptiques de matériaux en émission et réflexion depuis les températures cryogéniques jusqu'aux très hautes températures. Afin de dégager des lois générales sur l’émission de rayonnement d’un solide, il faut connaitre les paramètres fondamentaux : indice complexe, fréquence de relaxation, fréquence plasma sur le domaine le plus large possible à la fois en température mais aussi en longueur d’onde. Dans ce but une partie importante du travail de thèse a consisté à développer des moyens de mesure qui permettent d’effectuer des spectres d’émission ou de réflexion de l’ultraviolet à l’infrarouge lointain et pour les températures de 40K à 3000K.Une fois cet objectif atteint, un des premiers résultats fondamentaux a été d’étudier le zirconium à haute température. La multiplicité des montages nécessaires pour couvrir le domaine de mesure a permis ensuite des applications industrielles très variées, depuis la détermination du facteur d’absorption solaire du Kapton à 77K pour un satellite jusqu'à la cartographie en émissivité et température d’un bain de soudage d’acier. A température proche de l’ambiante la détermination de l’efficacité d’un isolant à bulles métallisé a conduit à mesurer et introduire dans les calculs les propriétés des matériaux dans l’infrarouge lointain. / This study deals with the thermo-optical properties of materials by emission and reflection from cryogenic temperatures up to very high temperatures.To identify the general laws of radiative emission of a solid, some basic parameters should be known: complex index, relaxation frequency, plasma frequency in a wide range of both temperatures and wavelengths. For this purpose, an important part of this work was to develop means to measure emission or reflection spectra from the ultraviolet to the far infrared and for temperatures from 40K to 3000K.When this is achieved, one of the earliest fundamental results was the study of zirconium at high temperature. Various experimentation was then used for a wide variety of industrial applications: from the determination of solar absorptance of Kapton at 77K for a satellite to the cartographies of emissivity and temperature for a bath of welding steel. In order to determine the insulation effectiveness of a bubble plating film near ambient temperature, measurement and introduction of material properties in the far infrared in the calculations have been conducted.

Neste trabalho, foram comparadas as cinéticas de adsorção da enolase (2-fosfo-D-glicerato hidrolase) sobre substratos hidrofílicos (placas de silício não modificadas ou silanizadas com aminopropilsilano (APS)) com aquelas sobre substratos hidrofóbicos (placas de silício silanizadas com trimetilclorosilano (TMCS) ou recobertas com filme de PS (poliestireno)). O efeito da forma do substrato (plano x esférico) sobre a cinética de adsorção também foi estudado. Os substratos esféricos foram esferas de vidro não modificadas (caráter hidrofílico) e silanizadas com TMCS (caráter hidrofóbico). As curvas de cinética de adsorção em substratos planos obtidas por elipsometria in situ mostraram que o processo ocorre em três etapas: (1) difusão das moléculas para a interface sólido/líquido, (2) formação de uma monocamada adsorvida e (3) adsorção de outras moléculas sobre a monocamada e formação de multicamadas. As isotermas mostraram que a enolase não possui adesão preferencial em substratos hidrofílicos ou hidrofóbicos. A etapa (1) pode ser descrita pelo modelo de adsorção seqüencial aleatória, enquanto que as etapas (2) e (3) podem ser descritas pelo modelo de adsorção seqüencial cooperativa. Não foi observada influência da força iônica. Contudo, imagens da topografia das superfícies recobertas por enolase obtidas por microscopia de força atômica (in situ e no ar) mostraram que os agregados de moléculas adsorvidas podem se apresentar na forma esférica (força iônica alta) ou como fibrilas (força iônica baixa). Medidas de espalhamento de raios-X a baixo ângulo (SAXS) de uma solução de enolase (6 g/L NaCl 0,001 mol/L) mostraram que as moléculas possuem raio de giro de 29 &#197;. Portanto, a agregação é induzida pelas propriedades da superfície da monocamada e pela força iônica do meio. Medidas de ângulo de contato mostraram que substratos inicialmente hidrofóbicos se tornaram hidrofílicos após adsorção da enolase, enquanto que os hidrofílicos apresentaram tendência oposta. Medidas de espectroscopia de fotoelétrons de raios-X evidenciaram que a adsorção sobre silício é mais rápida do que sobre PS, corroborando com os resultados obtidos por elipsometria. A influência do pH na adsorção da enolase em silício e APS mostraram que a adsorção é máxima quando o valor de pH é próximo ao ponto isoelétrico da enzima. A cinética de adsorção da enolase em substratos esféricos hidrofílicos e hidrofóbicos, acompanhada por espectrofotometria UV-vis, mostrou que a quantidade de material adsorvido O nestas superfícies aumenta com o tempo de adsorção e concentração inicial de enolase em solução (efeito de cooperativismo), sendo que o valor final é muito mais elevado nos substratos esféricos do que nos planos. Pela metodologia utilizada não se pôde observar os três estágios característicos da cinética de adsorção obtida para substratos planos. A influência da força iônica somente foi observada na adsorção sobre os substratos esféricos em sistemas concentrados (cenolase > 0,5g/L). As moléculas de enolase permanecem ativas após adsorção nos substratos estudados. / This work aimed to compare the adsorption behavior of enolase (2-phospho-D- glycerate hydrolase) onto hydrophilic (silicon wafers and amino-terminated surfaces (APS)) and hydrophobic planar substrates (polystyrene (PS) film, TMCS). The effect of the substrate shape (planar x spherical) was also studied. The spherical substrates were glass beads, native and modified with TMCS, with hydrophilic and hydrophobic characters, respectively. The adsorption kinetics of enolase onto planar substrates (obtained by means of in situ ellipsometry) presented three distinct regions: (i) a diffusion controlled step, (ii) monolayer formation evidenced by an adsorption plateau and (iii) continuous, irreversible and asymptotic increase of the adsorbed amount with time. The early stages were described by the random sequential adsorption model (RSA), while the cooperative sequential adsorption (CSA) model described regions (ii) and (iii). The adsorption isotherms show that enolase has no preferential adhesion onto hydrophilic or hydrophobic substrates. No significant influence of ionic strength was observed on the adsorption behavior of enolase onto the planar substrates. On the other hand, atomic force microscopy (AFM) showed that at long adsorption time and low ionic strength enolase monolayer induced fibrillation of the incoming molecules. Such effect was not observed at high ionic strength. Increasing the adsorption time, aggregates appeared on the surface, suggesting multilayer formation. Small angle X-ray scattering (SAXS) measurements of enolase (c = 6.0g/L) in NaCl 0.00 1 mol/L solution yielded radius of gyration of 29 &#197;, confirming that aggregation was probably induced by the surface of enolase monolayer and screening effects. Contact angle measurements showed that PS surfaces became hydrophilic and silicon surfaces turned hydrophobic after the formation of the enolase biofilm. XPS measurements showed that enolase adsorption is faster onto hydrophilic silicon wafers than onto hydrophobic PS fim, corroborating with the ellipsometric measurements. The study of the influence of pH on the enolase adsorption on silicon and APS surfaces showed that was the highest pH was close to the enzyme isoelectric point. The adsorption kinetic curves of enolase onto spherical substrates (obtained by means of UV-vis spectrophotometry) showed that the adsorbed amount (F) increased as function of adsorption time and initial concentration of enolase. The highest F value was obtained on spherical substrates. The three adsorption steps, characteristic of enolase adsorption, could not be observed by means of the methodology used. The influence of ionic strength was observed only in concentrated enolase solutions (cenolase 0.5g/L). The immobilized enolase molecules kept their enzymatic activity, regardless the type of substrate.

abstract: This thesis describes the fabrication of several new classes of Ge1-x-ySixSny materials with the required compositions and crystal quality to engineer the band gaps above and below that of elemental Ge (0.8 eV) in the near IR. The work initially focused on Ge1-x-ySixSny (1-5% Sn, 4-20% Si) materials grown on Ge(100) via gas-source epitaxy of Ge4H10, Si4H10 and SnD4. Both intrinsic and doped layers were produced with defect-free microstructure and viable thickness, allowing the fabrication of high-performance photodetectors. These exhibited low ideality factors, state-of-the-art dark current densities and adjustable absorption edges between 0.87 and 1.03 eV, indicating that the band gaps span a significant range above that of Ge. Next Sn-rich Ge1-x-ySixSny alloys (2-4% Si and 4-10% Sn) were fabricated directly on Si and were found to show significant optical emission using photoluminescence measurements, indicating that the alloys have direct band gaps below that of pure Ge in the range of 0.7-0.55 eV. A series of Sn-rich Ge1-x-ySixSny analogues (y>x) with fixed 3-4% Si content and progressively increasing Sn content in the 4-10% range were then grown on Ge buffered Si platforms for the purpose of improving the material's crystal quality. The films in this case exhibited lower defect densities than those grown on Si, allowing a meaningful study of both the direct and indirect gaps. The results show that the separation of the direct and indirect edges can be made smaller than in Ge even for non-negligible 3-4% Si content, confirming that with a suitable choice of Sn compositions the ternary Ge1-x-ySixSny reproduces all features of the electronic structure of binary Ge1-ySny, including the sought-after indirect-to-direct gap cross over. The above synthesis of optical quality Ge1-x-ySixSny on virtual Ge was made possible by the development of high quality Ge-on-Si buffers via chemical vapor deposition of Ge4H10. The resultant films exhibited structural and electrical properties significantly improved relative to state-of-the-art results obtained using conventional approaches. It was found that pure Ge4H10 facilitates the control of residual doping and enables p-i-n devices whose dark currents are not entirely determined by defects and whose zero-bias collection efficiencies are higher than those obtained from samples fabricated using alternative Ge-on-Si approaches. / Dissertation/Thesis / Ph.D. Physics 2013