Doctor of Philosophy / Department of Chemistry / Christine M. Aikens / Gold and silver particles with dimensions less than a nanometer possess unique characteristics and properties that are different from the properties of the bulk. They demonstrate a non–zero HOMO–LUMO gap that can reach up to 3.0 eV. These differences arise from size quantization effects in the metal core due to the small number of atoms. These nanoparticles have attracted great interest for decades both in fundamental and applied research. Small gold clusters protected by various types of ligands are of interest because ligands allow obtaining gold nanoclusters with given sizes, shapes and properties. Three main families of organic ligands are usually used for stabilization of gold nanoclusters: phosphine ligands, thiolate ligands and DNA. Usually, optical properties of these NPs are studied using optical absorption spectroscopy. Unfortunately, sometimes this type of spectrum is poorly resolved and tends to appear very similar for different complexes. In these cases, circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopy can be applied. However, the interpretation of experimental CD and MCD spectra is a complicated process. In this thesis, theoretically simulated CD and MCD spectra were combined with optical absorption spectra to study optical activity for octa– and nona– and undecanuclear gold clusters protected by mono– and bidentate phosphine ligands. Additionally, optical properties of bare and DNA protected silver NPs were studied. Theoretical CD spectra were examined to learn more about the origin of chirality in chiral organometallic complexes, and to contribute to the understanding of the difference in chiroptical activity of gold clusters stabilized by different phosphine ligands and DNA–stabilized silver clusters. Furthermore, optical properties of the small centered gold clusters Au₈(PPh₃)₈²⁺ and Au₉(PPh₃)₈³⁺ were examined by optical absorption and MCD spectra using TDDFT. Theoretical MCD spectra were also used to identify the plasmonic behavior of silver nanoparticles. These results showed that CD and MCD spectroscopy yield more detailed information about optical properties and electronic structure of the different chemical systems than optical absorption spectroscopy alone. Theoretical simulation of the CD and MCD spectra together with optical absorption spectra can be used to assist in the understanding of empirically measured CD and MCD and provide useful information about optical properties and electronic structure.

No description available.

Abstract In this work, phase structure and the surface morphology effects on the optical properties of nonlinear active nanocrystalline PZT thin films, with the high refractive index (n ≈ 2.5), were studied. A preliminary thickness-temperature map of the majority phase was presented, showing the dependence of room temperature deposited films thickness and post-annealing temperature on the crystallization and surface morphology. Changes in structural phase and surface morphology were found to define the optical properties of the films. The optical absorption edge shifted to shorter wavelengths with decreasing film thickness and post-annealing temperature, which led to an increase in band gap energies with ΔEg ≈ 0.55eV. Structural phase evolution induced surface effects caused the definite diffuse elements in the transmission spectra of the films. Low and evenly distributed scattering amplitudes in k-space were seen for single-phase oriented films with non-textured surfaces and led to low diffuse transmission values with TD ≈ 5%. Confined and increased scattering amplitudes in k-space were seen for films with phase co-existence, leading to microstructure-induced textured surfaces and increased diffuse transmission values with TD ≈ 50%. Diffuse transmission properties of the films were also calculated from surface profile data, using scalar scattering theory. The results showed very good agreement with the experimentally defined values. The difference between modelled and measured values was 3.8% at the maximum. Also changes in the surface morphology and crystal orientation were found to modulate the full width at half maximum Δβ values of the TE0 optical mode, indicating a strong dependence on the surface scattering process. Sharp optical mode widths Δβ ≈ 0.0048 and Δβ ≈ 0.0006, for single-phase oriented and amorphous-like films, respectively, were found. / Tiivistelmä Tässä työssä tutkittiin nanokiteisten korkean taitekertoimen (n ≈ 2.5) omaavien PZT ohutkalvojen optisten ominaisuuksien riippuvuutta ohutkalvon faasirakenteesta ja pinnan morfologiasta. Rakenneanalyysien perusteella muodostettiin paksuus-lämpötila faasikartta havainnollistamaan jälkihehkutuslämpötilan ja kalvon paksuuden vaikutuksia huoneenlämpötilassa pulssilaserkasvatusmenetelmällä kasvatettujen ohutkalvojen faasirakenteen ja pinnan morfologian muokkautumiseen. Muutokset kalvon faasirakenteessa ja pinnan morfologiassa määrittivät täysin kalvon optiset ominaisuudet siten, että optinen absorptioreuna siirtyi alemmille aallonpituuksille kalvon paksuuden ja jälkihehkutuslämpötilan pienentyessä, aiheuttaen energiaraon kasvun (ΔEg ≈ 0.55 eV). Faasirakenteen indusoiman pinnan morfologian muokkautuminen määritteli myös ohutkalvon sirontaspektrin yksityiskohdat aaltolukuavaruudessa. Tasaisesti jakautunut pienen amplitudin omaava sirontaspektri ja alhainen diffuusi sironta (TD ≈ 5 %) oli ominaista yksifaasisille, voimakkaasti orientoituneille ohutkalvoille, kun taas alhaisille aaltolukuarvoille rajoittunut korkean amplitudin omaava sirontaspektri ja lisääntynyt diffuusi sironta (TD ≈ 50 %) oli ominaista kaksifaasisille ohutkalvoille. Tutkittujen ohutkalvojen sirontaspektrin diffuusi komponentti laskettiin myös käyttäen skalaaria sirontateoriaa. Ero laskettujen ja mitattujen arvojen välillä oli maksimissaan 3.8 %. Muutokset ohutkalvojen pinnan morfologiassa ja faasirakenteessa havaittiin myös moduloivan optisen TE0 moodin puoliarvoleveyttä. Alhaisimmat pouoliarvoleveydet havaittiin yksifaasisilla (Δβ ≈ 0.0048) ja amorfisenkaltaisilla ohutkalvoilla (Δβ ≈ 0.0006).

D.Ing. (Electrical and Electronic Engineering) / Please refer to full text to view abstract

Using the Heyd-Scuseria-Ernzherof (HSE06) hybrid functional method along with photoluminescence experimental measurements, we analyze the properties of intrinsic defects such as vacancies, interstitials, antisites, and common complexes. By using configurational coordinate diagrams, we estimate the likelihood of defects to be radiative or non-radiative. Our calculations show that gallium vacancies exhibit a large magnetic moment in the neutral charge state and are most likely non-radiative. We also investigate the correlation between the observed infrared PL bands created in 2.5 MeV electron-irradiated GaN samples and the formation of native defects. It is found that gallium-nitrogen divacancies are possible sources of the broad PL band peaking at 0.95 eV while interstitial gallium is likely to be responsible for the narrow infrared PL band centered around 0.85 eV, with a phonon fine structure at 0.88 eV. In addition to native defects, we also investigate the blue luminescence band (BL2) peaking at 3.0 eV that is observed in high-resistivity GaN samples. Under extended ultraviolet (UV) light exposure, the BL2 band transforms into the yellow luminescence (YL) band with a maximum at 2.2 eV. Our calculations suggest that the BL2 band is related to a hydrogen-carbon defect complex, either CNON-Hi or CN-Hi. The complex creates defect transition level close to the valence band, which is responsible for the BL2 band. Under UV illumination, the complex dissociates, leaving as byproduct the source of the YL band (CNON or CN) and interstitial hydrogen. In conclusion, theoretical predictions of thermodynamic and optical transitions of defects in GaN via the HSE06 method, are found to be within less than 0.2 eV when compared to experiment. Hence the HSE formalism is a powerful tool for the identification and characterization of defects responsible for observed PL bands in GaN.

The presence of the hydrogen complex in Mg-doped GaN poses serious threats for the technological development of blue and ultraviolet light- emitting diodes and lasers. Since hydrogen is a difficult element to work with and it is incorporated into GaN through various mechanisms, a thorough understanding of hydrogen in GaN and other nitrides is essential to meet potential challenges by hydrogen. Most of the work done on the interaction of hydrogen implanted Mg-doped GaN deals mainly with passivation of the dopants and formation of the hydrogen complex with magnesium. However, the role of hydrogen implantation on the optical properties of Mg-doped GaN is not well understood. This study is mainly about optical properties of Mg-doped GaN and the effects of hydrogen on the Mg-doped GaN. Theoretically, group theory is used to determine the total number of symmetry allowed modes in GaN, Raman active modes and possible overtones. Experimentally, Raman and photoluminescence spectroscopy verify the theoretical results. / Dissertation (MSc)--University of Pretoria, 2006. / Physics / unrestricted

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Titan, la plus grosse lune de Saturne, est l'un des objets planétaires clé dans le domaine de l'exobiologie. Son atmosphère dense et riche en diazote est le siège d'une chimie organique intense. Ce travail de thèse se concentre sur les aérosols organiques produits dans son atmosphère. Ces derniers jouent un rôle essentiel dans l'évolution de l'atmosphère et de la surface du satellite mais aussi dans sa chimie organique d'intérêt exobiologique. Dans un premier temps, afin de disposer d'analogues de laboratoires (« tholins ») fiables de ces aérosols, un dispositif permettant d'obtenir des tholins propres a été développé, testé puis optimisé. Puis, deux aspects complémentaires des aérosols de Titan ont été étudiés :- Leurs propriétés optiques. En effet, la connaissance de ces dernières est indispensable, entre autres, pour l'analyse et l'interprétation des données d'observations de Titan. Une étude détaillée et critique de l'ensemble des données disponibles relatives aux indices de réfraction a été menée. Elle a permis de mettre en évidence les lacunes à combler. En parallèle, des mesures expérimentale ont permis de déterminer la matrice de diffusion à plusieurs longueurs et pour une large gamme d'angles de diffusion. Les résultats obtenus montrent que les tholins ne présentent pas une forme en agrégats comme les aérosols de Titan bien que les données acquises semblent bien représenter les données d'observations de Titan.- Leurs possibilités d'évolution chimique une fois à la surface, en particulier, la possible interaction des aérosols avec un cryomagma d'eau-ammoniaque. Des modèles de formation de Titan ont permis de déterminer une composition en sel de l'océan interne et de la cryolave. A partir de cette composition originale, une étude expérimentale de diverses hydrolyses des tholins a été effectuée. Les résultats obtenus montrent la formation de nombreux composés organiques dont des molécules d'intérêts exobiologiques, parmi elles, des espèces identifiées seulement en présence de sels. De plus, une liste des précurseurs potentiels de ces composés a été établie ce qui pourrait constituer une base de donnée pour la recherche de la composition chimique des tholins et/ou aérosols de Titan / Titan, the largest moon of Saturn, is one of the key planetary objects in the exobiology field. Its dense, nitrogen-rich atmosphere is the site of intense organic chemistry. This PhD work focuses on the organic aerosols which are produced in Titan's atmosphere. They play an important role in atmospheric and surface processes but also in its organic chemistry of exobiology interest. At first, in order to produce reliable laboratory analogs (“tholins”) of these aerosols, a device for the synthesis of clean tholins has been developed, tested and optimized. Then two complementary aspects of Titan aerosols have been studied :- Their optical properties. Indeed, their knowledge is prime importance to analyze and to better interpret many of Titan's observational data. A detailed and critical review of all available data on refractive indices was conducted. The lacks in this field have been highlighted. In parallel, direct experimental measurements were used to determine the scattering matrix at two wavelengths and for a wide range of scattering angles. The obtained results show that the tholins do not have the shape of aggregates such as Titan aerosols although the acquired data seem to match with observational data.- Their potential chemical evolution at Titan surface, in particular, the possible interaction between aerosols and putative ammonia-water cryomagma. Modelings of Titan formation have recently permitted the characterization of a composition in salts of the subsurface ocean and the cryolave. From this new and original chemical composition, a laboratory study of several hydrolyses of tholins has been carried out. The obtained results show the formation of many organic compounds, among them, species identified only in the presence of salts. In addition, a list of potential precursors of these compounds has been established

Black carbon (BC) is the light-absorbing component of soot, a combustion-generated aerosol that warms the climate by absorbing solar radiation. Its impacts on climate depend on its microphysical properties, which are modified by atmospheric processes including condensation, coagulation and wet removal. State of the art climate models consider soot in a concentric core/shell configuration, with a BC core coated by nonrefractory material such as organics or sulphate. Within this model, thicker coatings enhance visible light absorption, but also wet removal efficiency, and these have opposing effects on the total amount of light absorbed over BC’s lifetime. How well the core/shell model can calculate Mass Absorption Coefficient (MAC, the ratio of absorption to BC mass) is uncertain, as real soot forms more complex (often fractal) shapes, and detailed optical models using these morphologies predict the core/shell model may under- or over-estimate MAC depending on the precise properties of the particles. Few reliable measurements of variations in ambient MAC are available, as most older measurement techniques suffer from systematic uncertainties. In this work, a Single Particle Soot Photometer (SP2) and PhotoAcoustic Soot Spectrometer (PASS) were used to measure BC mass concentration and absorption, and these instruments do not suffer from such uncertainties. The SP2 was also used to report core size and coating thickness distributions that are required to test state of the art climate models. Firstly, a method was developed to minimise bias in the measured coating thicknesses related to the limited detection range of the SP2. The sensitivity of this technique to the assumed density and refractive index of the BC core was also explored, and the most appropriate parameters to use with ambient measurements were determined. Core and shell distributions were measured in Pasadena, California under a range of different photochemical ages. These were then used to calculate MAC, which was compared to that measured using the SP2 and PASS. The measured and modelled MAC agreed within 10% at 532 nm, though this was dependent on the assumed refractive index of the BC core. Overall MAC increased by 15 –25% in around one third of a day of photochemical ageing. This is quite modest compared to some climate models, but not compared to the previous best estimate, which predicted MAC may increase by a factor of ~1.5 over BC’s lifetime. Core and coating distributions were also measured in Canadian boreal biomass burning plumes. A case study was presented comparing the properties of BC in three plumes, one of which had passed through a precipitating cloud. It was demonstrated that larger and more coated BC-containing particles were removed more efficiently, in agreement with previous thermodynamic theory. By calculating MAC using the measured core/shell distributions and comparing to measured scattering, it was demonstrated that the MAC and single-scattering albedo in the plumes were likely not significantly affected by the wet removal, as greater differences were observed between the two plumes not affected by precipitation.

Opto-electronic semiconductor technology continues to grow at an accelerated pace, as the industry seeks to perfect devices such as light emitting diodes for purposes of optical processing and communication. A strive for greater efficiency with shrinking device dimensions, continually pushes the technology from both a design and materials aspect. Nanosystems such a quantum dots, also face new material engineering challenges as they enter the realm of quantum mechanics, with each system and material having markedly different electronic properties. Traditionally, the semiconductor industry has focused on materials such Group II-VI and III-V compounds as the basis material for future opto-electronic needs. Unfortunately, these material systems can be expensive and have difficulties integrating into current Si-based technology. The industry is reluctant to leave silicon due in part to silicon's high quality oxide, and the enormous amount of research invested into silicon based circuit fabrication. Although recently materials such as GaN are starting to dominate the electro-optical industry since a Si-based substitute has not been found. The purpose of the dissertation was to examine several promising systems that could be easily integrated into current Si-based technology and also be produced using simple inexpensive fabrication techniques such ion implantation. The development of optically active nano-sized precipitates in silica to form the active layer of an opto-electronic device was achieved with ion implantation and thermal annealing. Three material systems were investigated. These systems consisted of carbon, silicon and metal silicide based nanocrystals. The physical morphology and electronic properties were monitored using a variety of material characterization techniques. Rutherford backscattering/channeling were used to monitor elemental concentrations, photoluminescence was used to monitor the opto-electronic properties and transmission electron microscopy was used to study the intricate morphology of individual precipitates. The electronic properties and the morphology were studied as a function of implant dose, anneal times and anneal temperatures.