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M. Ing. (Electronic and Electrical) / Porous silicon has been obtained by anodizing monocrystalline silicon in hydrofluoric acid solutions. The experimental conditions needed to obtain this material are described. A scanning electron microscopy study revealed the morphology of the pores. The diffusion-limited model is the current accepted model explaining the formation of porous silicon. The structure of porous silicon formed on lightly doped n-type silicon does, however, not agree with the morphologies predicted by the basic model. The model was·therefore extended to include the n-type observations. The observed straight pores, the fluctuation of pore length and the double layered structure were succesfully simulated. Visible photoluminescence were obtained from p-type porous silicon. The properties of the emitted light were investigated together with the quantum confinement and siloxene models describing this behaviour of porous silicon. The effect of the anodizing parameters on the electroluminescence visible during the anodic oxidation of porous silicon were investigated leading to additional proof of the quantum confinement model. A model describing the band structure of the silicon-electrolyte system during electroluminescence is proposed.

Photovoltaics is an exciting area of research with the potential to completely change the world's energy landscape. Silicon still dominates the photovoltaics market and shows no sign of being overtaken by other materials systems for large scale manufacture. Huge strides have been made in recent years to reduce the cost of solar modules, mainly through the introduction of mass production solar panel plants. However producing very pure single crystalline silicon is still a relatively expensive, energy intensive process. If cheaper less pure silicon could be cast into multi-crystalline ingots, without significant losses to the conversion efficiency this could be a game changer in the photovoltaics industry. For this to happen we need to have greater knowledge and understanding of the role of metallic impurities in solar silicon. If we can find ways to passivate or getter these impurities in cost effective processes that lend themselves to mass production then this would be the key to cost effective solar energy. In the work in this thesis I have investigated some of the most common and most harmful metallic impurities in silicon solar cells using a combination of Deep Level Transient Spectroscopy (DLTS), Capacitance Voltage (CV) measurements, Secondary Ion Mass Spectroscopy and Tunnelling Electron Microscopy (TEM). The specific transition metals I studied were iron, as it is one of the most common impurities and also titanium and molybdenum, because they are very harmful, have slow diffusivities and hard to get rid of with traditional gettering techniques. I have then looked at using hydrogen to electrically passivate these defects, and show evidence that hydrogen passivation is possible for interstitially incorporated titanium in silicon, but is unlikely to happen for interstitially incorporated iron. Another important part of this thesis was the observation and characterisation of molybdenum nano-precipitates in silicon. We have observed the nano-precipitates both electrically in DLTS, and physically in TEM. The precipitates have very interesting electrical properties, and appear to be very strong minority carrier recombination centres, which would have a very negative effect on solar cell performance. It is possible that these nano-precipitates could form from any of the slow diffusing transition metals, and could be a key reason to explain the efficiency gap between low purity cast silicon and high purity single crystal silicon.

M.Sc. (Physics) / Silicon thin films can be manufactured with the aid of various deposition techniques, each with its own unique properties. In this study the optical properties of silicon manufactured with physical vapour deposition from an electron beam source were studied as a function of layer thickness, deposition rate and substrate temperature. The index of refraction (n and k) as well as optical gap eg. were determined with the aid of characterization models derived specific for optical techniques. These models are covered extensively in the thesis. It was found that the layers were homogeneous and stable, but that the deposition rate and substrate temperature did have a large influence on the properties of the layers. The results show that structural changes, first from the collumnar structure to an amorphous structure and with a further increase in substrate temperature, also a transition from the amorphous to a microcrystalline structure do occure at temperatures considerably lower than what was previously anticipated. With variations in deposition rate it was found that the disorder in the coating will increase with an increase in rate resulting in a reverse transition from the microcrystalline structure to the amorphous structure. Optical gaps in the range 1. 12eV to approximately 1. 38eV were found to be possible with the correct choice of deposition parameters...

Magister Scientiae - MSc / The growth of amorphous hydrogenated silicon (a-Si:H) thin films deposided by hot wire chemical vapor deposition (HWCVD) has been studied. The films have been characterised for optical and structural properties by means of UV/VIS,FITR,ERDA, XRD.XTEM and Raman spectroscopy. Low subtrate heater temperatures in the range form 130 to 200 degrees celcius were used in this thesis because it is believed to allow for the deposition of device quality a-Si:H which can be used for electronic photovoltaic devices. Furthermore, low temperatures allows the deposition of a-Si:H on any subtrate and thus offers the possibility of making large area devices on flexible organic substances. We showed that the optical and structural properties of grown a-Si:H films depended critically upon whether the films were produced with silane gas or silane diluted with hydrogen gas. We also showed that it is possible to to deposit crystalline materials at low temperature under high hydrogen dilution ratio of silane gas. / South Africa

This dissertation focuses on the characterization of hydrogen implanted 3C-SiC and helium implanted 6H-SiC and the interaction of silver and palladium with the SiC. The main technique used for the analysis of the implanted SiC was transmission electron microscopy (TEM), although scanning electron microscopy (SEM) and nanoindentation hardness testing were also used. Both H and He implantations were done at an ion energy of 100 keV and the total dose for both species was 1017 ions/cm2. Specimens were annealed at 1000 °C for 20 min in an inert atmosphere. The observed depth of ion damage agreed closely with that predicted by TRIM 2008. The damaged region in the He implanted specimens had a high density of small bubbles but no cracks were observed. Severe cracking was observed along the damaged region in the H implanted specimens. A second phase hexagonal (4H-SiC) was detected in two grains in the 3C-SiC and some grown in voids were also observed. The wettability of SiC by a 2:1 by volume mixture of Ag and Pd is extremely low but is significantly increased through the addition of Si to the mixture. The Si containing metal mixture was found to migrate along the grain boundaries of polycrystalline 3CSiC while sealing the point of entry. Pd attacks SiC and severe etching was observed on the surface of 6H-SiC. An epitaxially orientated Pd2Si inclusion was observed in the 6H-SiC. No effect of implantation damage on the interaction of Pd and Ag with SiC was observed. Pd etched the surface of the He implanted 6H-SiC down through the damaged region with no evidence of implantation damage left after 67 hours of annealing and thus no conclusions could be drawn. The metal mixture interacted with the non implanted surface of the H implanted 3C-SiC after dissolving the Si substrate and therefore the effect of the ion damage on the interaction could not be investigated. Nanoindentation hardness measurements showed a marked increase in hardness of He implanted 6H-SiC annealed for 20 min at 1000 °C over that of as implanted and virgin material. There was also a large decrease in hardness corresponding to the depth of the ion damage.

This thesis describes the key steps in the production of high purity (solar-grade) silicon from metallurgical-grade silicon for use in the production of photovoltaic cells as alternative renewable, environmentally benign and cheap energy source. The initial part of the project involves the development and optimization of a small chemical production platform system capable of producing alkoxysilanes from metallurgical-grade silicon as green precursors to solar-grade silicon production. Specifically, the main aim of the study was to synthesize trialkoxysilanes in continuous flow mode, although the synthesis on monosilane was also done in batch mode. The alkoxylation reaction was carried out in a traditional slurry phase batch reactor, packed bed flow tubular reactor and also attempted in a continuous flow falling film tubular reactor. The effect of key parameters which affect the silicon conversion and selectivity for the desired trialkoxysilane were investigated and optimized using ethanol as a reagent model. The synthesis was then extended to the other alcohols namely methanol, n-propanol and n-butanol. Copper catalysts which were tested in the alkoxylation reaction included: CuCl, Cu(OH)2, CuO and CuSO4. CuCl and Cu(OH)2 showed comparable activity in the batch mode but the former was more efficient in the packed bed flow tubular reactor. Cu(OH)2 could be used as a non-halide catalyst but its activity is limited to short reaction cycles (<10 h). The uncatalysed reaction resulted in negligible reaction rates in both types of reactors. High temperature catalyst pre-heating (>500 oC) resulted in a lower rate of reaction and selectivity than when slightly lower temperatures are used (<350 oC) in both reactors, although much difference was noticed in the packed bed flow tubular reactor. Synthesis in the batch reactor needed longer silicon-catalyst activation time, higher pre-heating temperature and higher catalyst amounts as compare to the packed bed flow tubular reactor. Reaction temperature and alcohol flow rate influenced the reaction in both methods. The optimum reaction temperature range and alcohol flow rate was comparable in both reactors (230 to 240 oC) and 0.1mL/min respectively. The effect of alcohol R-group (C1 to C4) on the reaction revealed that conversion and selectivity generally decrease with an increase in carbon chain length in both methods. Ethanol showed highest selectivity (>95% in batch and >97% in flow) and conversion (about 88% in batch and about 64% in flow) as compared to all other alcohols studied showing that it could be the most efficient alkoxylation alcohol for this reaction. Overally, the packed bed flow tubular reactor resulted in higher selectivity to trialkoxysilanes than the batch system. Performing the reaction under pressure resulted in increased conversion but selectivity to the desire trialkoxysilane diminished. Synthesis in a continuous flow falling film tubular reactor was not successful as it resulted in very poor conversion and selectivity. Monosilane was successfully synthesized from the disproportionation of triethoxysilane using homogeneous and heterogeneous catalysts in batch mode. The results obtained from homogeneous catalysis showed that the reaction can be conducted at room temperature. The heterogeneous catalysis method resulted in slow conversion at room temperature but mild heating up to 55 oC greatly improved the reaction. Conducting the reaction under neat conditions produced comparable results to reactions which were carried out using solvents. The disproportionation reaction was best described by the first order kinetic model. The results obtained in this research indicate that the packed bed flow tubular reactor can be utilized with future modifications for continuous flow synthesis of alkoxysilanes as feedstock for the solar-grade silicon production.

This dissertation focuses on an electron microscopy investigation of the microstructure of SiC layers in TRISO coated particles deposited by chemical vapour deposition under different experimental conditions, which include temperature, concentration of gases and deposition time. The polycrystalline β-SiC was deposited from the decomposition of methyl trichlorosilane MTS in the presence of hydrogen (H2) as carrier gas. Scanning electron microscopy (SEM), using the backscattered electron (BSE) mode, was used to image the microstructure of and defects in the SiC layers of TRISO particles. Electron backscatter diffraction (EBSD) in the SEM was used to determine the SiC grain sizes and distribution thereof in TRISO particles deposited under different conditions. For samples with a poor EBSD indexing rate, transmission Kikuchi diffraction and transmission electron microscopy (TEM) investigations were also carried out. From the results, the effects of growth temperature on the SiC microstructure, specifically on the grain size and shape and the porosity were determined. The effects of cooling or non-cooling of the gas inlet nozzle on the SiC microstructure were also investigated. TEM and scanning TEM (STEM) analyses of the SiC layers in TRISO particles were performed to image the defects and reveal the crystallinity of SiC layers. The microstructure and composition of SiC tubes fabricated by reaction bonding (RB) was also investigated by using electron microscopy and Raman spectroscopy. SEM-BSE imaging of RBSiC samples allowed the identification of impurities and free silicon in the RBSiC. Finally, the penetration of the metallic fission product, palladium, in reaction bonded SiC at a temperature of a 1000ºC is determined. A brief comment on the suitability of RBSiC as candidate for fuel cladding in a PWR is made. A short discussion of the suitability of the characterisation techniques used is included at the end.

The optical absorption line is 1s₁- 2p₀ at the absorption spectrum of arsenic doped silicon has been studied for various arsenic concentrations at four temperatures. The concentrations are .9 x 10¹⁵ cm⁻³, 1.7 x 10¹⁵ cm⁻³, 4.0 x 10¹⁵ cm⁻³ and 1.5 x 10¹⁶ cm⁻³, the temperatures are 4.2°K, 53°K, 77°K, and 90°K. Spectrometer broadening was accounted for in the observed line-widths. There was observed two temperature independent broadening mechanisms, concentration and strain broadening. Two temperature dependent broadening mechanisms were observed, phonon broadening and the statistical Stark effect. The five, broadening mechanisms are believed to account for the total line-width through the use of the Voigt analysis half-breadth method. A shift of the peak position with temperature was noted and a possible explanation presented. / Science, Faculty of / Physics and Astronomy, Department of / Graduate