Philosophiae Doctor - PhD / Nanocrystalline silicon (nc-Si:H) is an interesting type of silicon with superior electrical properties that are more stable compared to amorphous silicon (a-Si:H). Silicon nitride (SiNₓ) thin films are currently the dielectric widely applied in the microelectronics industry and are also effective antireflective and passivating layers for multicrystalline silicon solar cells. Research into the synthesis and characterization of nc-Si:H and SiNₓ thin films is vital from a renewable energy aspect. In this thesis we investigated the film growth mechanisms and the filament stability during the hot-wire chemical vapour deposition (HWCVD) of nc-Si:H and SiNₓ thin films. During the HWCVD of nc-Si:H, electron backscatter diffraction (EBSD) revealed that the tantalum (Ta) filament aged to consists of a recrystallized Ta-core with Ta-rich silicides at the hotter centre regions and Si-rich Ta-silicides at the cooler ends nearer to the electrical contacts. The growth of nc-Si:H by HWCVD is controlled by surface reactions before and beyond the transition from a-Si:H to nc-Si:H. During the transition, the diffusion of hydrogen (H) within the film is proposed to be the reaction controlling step. The deposition pressure influenced the structural, mechanical and optical properties of nc-Si:H films mostly when the film thickness is below 250 nm. The film stress, optical band gap, refractive index and crystalline volume fraction approached similar values at longer deposition times irrespective of the deposition pressure. Filament degradation occurred during the HWCVD of SiNₓ thin films from low total flow rate SiH₄ / ammonia (NH₃) / H₂ gas mixture. Similar to the HWCVD of nc-Si:H, the Ta-core recrystallized and silicides formed around the perimeter. However, Tanitrides formed within the filament bulk. The extent of nitride and silicide formation, porosity and cracks were all enhanced at the hotter centre regions, where filament failure eventually occurred. We also applied HWCVD to deposit transparent, low reflective and hydrogen containing SiNₓ thin films at total gas flow rates less than 31 sccm with NH₃ flow rates as low as 3 sccm. Fluctuations within the SiNₓ thin film growth rates were attributed to the depletion of growth species (Si, N, and H) from the ambient and their incorporation within the filament during its degradation.

M.Phil. / Linearly chirped fibre Bragg gratings can be used to compensate dispersions in a fibre transmission system. Various methods have been developed to chirp fibre gratings. It is proposed that a uniform period grating can be chirped by applying an axially linear strain gradient. In this project, we shall demonstate a novel method for making chirped fibre Bragg gratings, which involves bonding an unchirped fibre Bragg grating of 5cm length to the surface of a tapered stainless steel plate which is strained by bending or dilating. This allows a strain gradient to be formed along the grating length through the transferring of strains from the plate to the fibre. The profiles of tapered stainless steel plates have been determined by means of the finite element method and computer simulations to establish the strain gradient during loading. Ten conventional resistive strain gauges are also bonded on the other surface for strain measurements. Because of the strain gradient, the local Bragg wavelength is a function of the position along the length of the fibre grating so that the grating chirp is an automatic consequence of the strain gradient. This method provides the dynamic control of Bragg wavelength shift, peak reflectivity and spectral bandwidth, and its tunability is also suitable for optimising pulse compression and optical fibre dispersion compensation. Using couple-mode equations, we have also calculated the reflection response of a chirped fibre grating. It is shown that the close agreement between the theoretical and the experimental results suggests that the strain gradient technique provides good control of the Bragg grating chirp and the center wavelength of a chirped fibre Bragg grating.

M.Ing. / Fibre Bragg gratings (FBGs) have been manufactured for the first time in South Africa by means of the phase mask method. It is possible to manufacture not only uniform FBGs, but also chirped FBGs. The optical fibre that is used for imprinting the FBGs can also be hydrogen loaded locally. FBGs with a reflectivity of 99.7% and higher can be written by making use of the experimental setup presented in this thesis. It is possible to manufacture a FBG with a centre wavelength that has any value between the Bragg wavelength and approximately 6 nm lower than the Bragg wavelength. This is done by stretching the optical fibre prior to the writing process. FBGs have been simulated in MATLAB to get an idea of what one may expect during the manufacturing process. The program makes it possible to simulate the effects of changes in grating length, index modulation, pressure, temperature and strain on the centre wavelength of an FBG. Dispersion is explained in detail. Chromatic dispersion, which is part of dispersion as a whole, can be cancelled by making use of an FBG. The different techniques for the measurement of chromatic dispersion is explained. Some insight is given on dispersion (the pulse broadening in the time domain due to the different velocities of different wavelengths from the source's finite optical bandwidth) compensation. An FBG that was manufactured locally has been tested as a dispersion compensator. It was found that an FBG is effective in performing this function.

We are presenting an overview of MEMS-based (Micro-Electro-Mechanical System) optical switch technology starting from the reflective two-dimensional (2D) and three-dimensional (3D) MEMS implementations. To further increase the speed of the MEMS from these devices, the mirror size needs to be reduced. Small mirror size prevents efficient reflection but favors a diffraction-based approach. Two implementations have been demonstrated, one using the Texas Instruments DLP (Digital Light Processing), and the other an LCoS-based (Liquid Crystal on Silicon) SLM (Spatial Light Modulator). These switches demonstrated the benefit of diffraction, by independently achieving high speed, efficiency, and high number of ports. We also demonstrated for the first time that PSK (Phase Shift Keying) modulation format can be used with diffraction-based devices. To be truly effective in diffraction mode, the MEMS pixels should modulate the phase of the incident light. We are presenting our past and current efforts to manufacture a new type of MEMS where the pixels are moving in the vertical direction. The original structure is a 32 x 32 phase modulator array with high contrast grating pixels, and we are introducing a new sub-wavelength linear array capable of a 310 kHz modulation rate.

No description available.

The measurement of strain is critical in many engineering design, test, and health monitoring procedures. Despite the promise of non-contacting and remote strain measurement, optical techniques have not been widely adopted by industry; the preference being the use of electrical resistance strain gauges. This is due to the perceived and real complexities of many optical techniques.

Inelastic neutron scattering measurements by Okazaki, Tuberfield, and Stevenson (1964) of the antiferromagnetic spin wave energy, spectrum in manganese fluoride crystal at low temperatures, agree with the results predicted by a dispersion relation introduced without proof in their paper. In this thesis the question is considered in detail to what extent this dispersion relation is justified. The interaction between the manganese ions is described by the Heisenberg exchange Hamiltonian. Following Holstein and Primakoff's formalism the spin deviation operators are introduced and the part of the Hamiltonian ℋ[superscript B] containing all the terms up to those bilinear in the spin deviation operators is diagonalised by means of the Anderson transformation. A correction is next obtained by retaining the diagonal part of those terms which are quadrilinear in the spin deviation operators. Under certain conditions it is shown that ℋ[superscript B] together with the correction term give rise to, a dispersion relation which is identical with that used by Okazaki et al. (1964). Finally the validity of the approximations is also discussed. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

La méthode solide-liquide en milieu alliage fondu à base de lithium a permis ces dernières années la synthèse de plusieurs composés d'intercalation du graphite (CIG) insérés à coeur au sein des systèmes graphite-lithium-alcalino-terreux. Dans le cadre de cette thèse, cette méthode de synthèse a été étendue aux systèmes graphite-lithium-lanthanoïde, avec une difficulté supplémentaire qui est la méconnaissance des diagrammes de phases binaires lithium-lanthanoïde dont les données sont capitales pour déterminer les domaines de température et de composition chimique des alliages susceptibles de conduire à des CIG. L'immersion de plaquettes de pyrographite dans certains alliages lithium-europium judicieusement choisis a mené à un composé binaire EuC6 ainsi qu'à un composé ternaire graphite-lithium-europium de premier stade.La cinétique de formation de EuC6 a été suivie par diffraction des rayons X ex situ afin de comprendre les différentes étapes de la réaction et d'identifier les phases intermédiaires menant au composé final thermodynamiquement stable. Ce mécanisme révèle un processus réactionnel plus « coopératif » que celui menant au composé CaC6 et a été décrit par une succession d'étapes contribuant à l'insertion à coeur de l'europium.La composition élémentaire du composé ternaire a été déterminée grâce à une analyse par faisceau d'ions qui a permis de doser simultanément les trois éléments lithium, carbone et europium. Le résultat de cette analyse a conduit à la formule chimique Li0,25Eu1,95C6. EuC6 a également été étudié par microsonde nucléaire, le rapport atomique C/Eu de 6 a ainsi notamment pu être confirmé.Des études structurales ont été menées pour les composés binaires et ternaires. D'une part, il a été possible d'effectuer la résolution structurale complète du binaire EuC6, qui cristallise dans une maille hexagonale de groupe d'espace P63/mmc. D'autre part pour le ternaire Li0,25Eu1,95C6, la séquence d'empilement poly-couche selon l'axe c du feuillet inséré a été modélisée, par combinaison des données structurales avec les informations issues de l'analyse par faisceau d'ions.Les composés d'intercalation du graphite sont des solides de basse dimensionnalité qui se prêtent idéalement à l'étude des relations structure-propriétés. Ainsi dans le système graphite-lithium-calcium, le caractère supraconducteur des composés CaC6 et Li3Ca2C6 a été étudié par spectroscopie de spin de muon ([mu]SR). Pour le système graphite-lithium-europium, des mesures magnétiques réalisées préalablement à ce travail ont été poursuivies et complétées par des analyses [mu]SR (pour Li0,25Eu1,95C6 et EuC6) ainsi que par spectrométrie Mössbauer de 151Eu (pour Li0,25Eu1,95C6) à basse température. / The molten alloy solid-liquid method containing lithium has recently enabled the synthesis of several bulk graphite intercalation compounds (GICs) in graphite-lithium-alkaline earth metal systems. As part of this thesis, this synthesis method was extended to graphite-lithium-lanthanide systems, with an additional difficulty which is the lack of knowledge of lithium-lanthanide binary phase diagrams whose data are crucial for determining the temperature range and chemical composition of alloys that may lead to GICs.The immersion of pyrographite platelets in some europium-lithium alloys wisely chosen led to a binary EuC6 compound as well as a graphite-lithium-europium first stage ternary compound.Kinetics study of EuC6 compound was followed by ex situ X-ray diffraction in order to understand the different reaction steps and identify intermediate phases leading to the thermodynamically stable final compound. This mechanism revealed a reaction process more "cooperative" than that leading to CaC6 binary compound and was described by a succession of steps that contribute to the bulk insertion of europium.The elementary composition of the ternary compound was determined by ions beam analysis allowing the simultaneous quantification of the three elements lithium, carbon and europium. The refinement of these analyses led to the chemical formula Li0,25Eu1,95C6 for the ternary compound. EuC6 has also been studied by nuclear microprobe analysis, and especially the C/Eu atomic ratio equal to 6 has been confirmed.Structural studies have been undertaken for binary and ternary compounds. On one hand, it was possible to fully resolve the three-dimensional structure of the binary EuC6, which crystallizes in a hexagonal unit cell with P63/mmc space group. On the other hand, the c axis stacking sequence of the poly-layered intercalated sheet of the ternary compound was modeled by combining structural data with information from the ions beam analysis. The graphite intercalation compounds are low-dimensional solids that are ideal for the study of structure-properties relations. Thus in graphite-lithium-calcium system, superconducting character has been studied for CaC6 and Li3Ca2C6 compounds by muons spin spectroscopy ([mu]SR). For the graphite-lithium-europium system, previous magnetic measurements have been continued and supplemented by [mu]SR analysis (for Li0,25Eu1,95C6 and EuC6) and by low temperature 151Eu Mössbauer spectroscopy (for Li0,25Eu1,95C6).

The initial aim of the work presented in this thesis was to examine smectic layer compressibility with a view to improving our understanding of the stability of intermediate phases. A natural starting point was to investigate the smectic-A phase, as it is the most basic of the smectic phases. The response of the layered structure to external fields is also a focus of this thesis as electric and magnetic fields enable the layer properties to be probed. Investigations into the reorientation dynamics of smectic-A layers in magnetic fields were performed using geometries and cell thicknesses (>50 μm) that are not feasible using electric fields. Data presented in this thesis show that three distinct reorientation mechanisms can occur, one of which is previously unreported and bridges the gap between the previously known mechanisms. The new mechanism observed in 270 μm and 340 μm thickness cells exhibits multiple stage reorientation on a timescale between tens and hundreds of seconds. Using conventional electro-optic techniques combined with a theoretical approach developed by others, this thesis presents a new technique to provide measurement of relative smectic layer compressibility of eight smectic-A liquid crystalline materials. The method presented here combines data on cell thickness, dielectric anisotropy and the measurement of the voltage threshold of the toroidal to stripe domain transition. As expected, the experimental data indicated that materials with shorter molecular lengths had the largest relative layer compressibility. Finally, direct measurement of smectic layer compressibility was investigated and the design of an apparatus capable of such measurements was undertaken. Preliminary results from such an apparatus are presented along with a discussion on the steps taken to develop the design.

This thesis consists of the structures of two compounds as determined by single crystal x-ray diffraction. The first structure is that of a phosphazene - iodine complex: hexamethylcyclotriphosphazene - iodine (1:1 adduct) and the second structure is the redetermination of sodium formate. Crystals of hexamethylcyclotriphosphazene - iodine (1:1 adduct) are triclinic, a = 10.707(13), b = 8.873 (5), c = 8.871(6)Å, α = 96. 65 (6), β = 103.91 (12), ɤ = 97.81(12)°, Z = 2, space-group PI. The structure was determined with Mo-K« diffractometer data by Patterson and Fourier synthesis, and was refined by full-matrix least-squares calculations to R = 0.053 for 1934 observed reflexions. The iodine molecule is weakly bonded to a nitrogen atom on the phosphazene ring, N - I = 2.417(7), I - I = 2. 823 (1) Å, N - I - I = 177.8(2)°. The six-membered phosphazene ring is slightly, but significantly, ncn-planar, the conformation being that of a chair. The molecule has pseudo-m symmetry. Two distinct P-N bonds are present; the longer ones, mean P - N = 1.64 Å, involve the nitrogen that is weakly bonded to the iodine molecule, while the other four P-N bonds are equivalent, mean P - N = 1.598 Å. All the P - C bonds are equivalent, mean P - C = 1.789 Å. The mean endocyclic N - P - N and P - N - P angles are 114.7 and 124.0° respectively, while the mean exocyclic C - P - C angle is 104°. Crystals of sodium formate are mcnoclinic, a = 6.2590 (6), b = 6.7573 (16) , c = 6.716 (5) Å, β = 116.140(6)°, Z = 4, space-grcup C2/c. The structure was determined by direct methods, and was refined by electron density and full-matrix least-squares procedures to E = 0.022 for 250 reflexions. Sodium formate is planar and has C2V symmetry. Partial charges were refined on the formate ion. The partial charges found on each atom are as follows: 0 -0.23(1)e, C +0.16(3)e, H -0.49(10)e, and Sa +0.79(14)e. The sodium ion has six oxygen neighbours at an average distance of 2.45 Å and there are weak Na. ..0 interactions. There is a C - H...Na hydrogen bond which forms continuous rows of sodium formate ions. The C - 0 bond distance is 1.246(1)Å and the 0 - C - 0 angle is 126.3(2)°. / Science, Faculty of / Chemistry, Department of / Graduate