Thesis (MSc)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: Silicone rubber, particularly poly(dimethylsiloxane) (PDMS), has been increasingly used in the manufacture of outdoor high voltage insulators in the recent years. PDMS offers several advantages that make it suitable for outdoor use, such as low weight, a hydrophobic surface, stability, and excellent performance in heavily polluted environments. PDMS surfaces can, however, become progressively hydrophilic due to surface oxidation caused by corona discharge, UV radiation and acid rain. In this study, PDMS samples of controlled formulations as well as six commercial insulator materials four PDMS based and two ethylene propylene diene monomer (EPDM) based were exposed to various accelerated weathering conditions for various periods of time in order to track changes in the material over time. The ageing regimes developed and used to simulate the potential surface degradation that may occur during in-service usage included needle corona and French corona ageing, thermal ageing, UV-B irradiation (up to 8000 hours) and acid rain (up to 200 days). Both the chemical and physical changes in the materials were monitored using a wide range of analytical techniques, including: static contact angle measurements (SCA), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), gas chromatography (GC), gas chromatography/mass spectroscopy (GC/MS), size-exclusion chromatography (SEC), Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS) and slow positron beam techniques (PAS). A low molecular weight (LMW) uncrosslinked PDMS model compound was used to further study the chemical effects of corona exposure on PDMS materials. PDMS showed far better performance than EPDM, in terms of resistance to the various ageing regimes and “hydrophobicity recovery”. / AFRIKAANSE OPSOMMING: Silikoonrubber, spesifiek polidimetielsiloksaan (PDMS), is gedurende die afgelope paar jaar toenemend gebruik in die vervaardiging van buitelughoogspanningisolators. PDMS het baie voordele vir gebruik in elektriese isolators soos ‘n laer massa, ʼn hidrofobiese oppervlak, stabiliteit en uitstekende werking in hoogsbesoedelde omgewings. Die hidrofobiese oppervlakte kan egter gelydelik hidrofilies word weens oppervlakoksidasie as gevolg van korona-ontlading, UV-bestraling en suurreën. In hierdie studie is PDMS monsters van verskillende samestellings sowel as ses kommersiële isolators (vier PDMS en twee etileenpropileenrubber (EPDM)) blootgestel aan verskillende versnelde weersomstandighede vir verskillende periodes om die veranderinge in die materiale te monitor. Die verskillende materiale is gerangskik volgens hulle werking oor ‘n periode van tyd. Dit het ook ‘n geleentheid gebied om die eienskappe van die verskillende samestellings te bestudeer. Die tegnieke wat ontwikkel is om die moontlike oppervlakdegradasie te simuleer, het naald-korona, “French” korona, UVB-bestraling (tot 8000 uur) en suurreën (tot 200 dae) ingesluit. Beide die chemiese en die fisiese veranderinge in die materiale is gemonitor met behulp van verskeie tegnieke soos statiese kontakhoekbepaling, optiese mikroskopie, skandeerelektronmikroskopie, energieverspreidingsspektroskopie, gaschromatografie, grootte-uitsluitingschromatografie, foto-akoestiese Fouriertransforminfrarooi (PASFTIR) en stadige-positronspektroskopie (PAS). ʼn Lae molekulêre massa PDMS modelverbinding is gebruik om die chemiese effek van korona te bestudeer. Die PDMS materiale het baie beter vertoon teenoor die EPDM materiale in terme van hulle herstel van hidrofobisiteit.

This thesis presents an investigation into a wide range of potential materials for organic photovoltaic (PV) devices. A variety of optical techniques are used to define physical parameters for each material such as the photoluminescence quantum yield (PLQY), absorption coefficient and exciton diffusion length. Electrical characterisation is used to determine the optimal structure for devices fabricated with these materials. A number of novel materials are presented in this thesis. These include new polymers, both soluble and precursor, and a relatively new class of material, the conjugated dendrimer. These are highly configurable branching molecular structures that enable fine tuning of material properties. Work on polymers presented in this thesis investigates how such materials can be improved by testing the effect of small changes to their molecular structure. One of these changes had significant effects upon the overall material characteristics. The introduction of a dipole across a polymer successfully created a charge separating material without the need for an extra species such as C60 to be present. The introduction of the conjugated dendrimer to PV applications allows significant scope for molecular engineering. Dendrimers enable tight control over certain aspects of the molecular properties. Small changes can be made such as colour tuning or solubility that enable optimisation to be performed on the molecular level, rather than on device structure. Such changes produced significantly higher internal quantum efficiencies (> 90%) than typical polymer devices and offer the prospect of power conversion efficiencies in excess of 10%. Time-resolved luminescence (TRL) spectroscopy was used to characterise the behaviour of photogenerated excitons within organic films. The investigation of exciton diffusion length was performed upon two polymers, each utilising two different time-resolved methods; diffusion to a quencher and exciton-exciton annihilation. It was found that diffusion in polythiophene films is anisotropic and the photoluminescence lifetime is dependent upon film thickness. This is explained by the formation of self-ordered microstructures during the spin coating process. Data modelling was performed which took into account both the thickness variation and the interaction of excitons with a quenching interface producing a much more realistic approach than previously published work.

This thesis presents a study of lasing properties and optical amplification in semiconducting conjugated polymers and dendrimers. Configured as surface-emitting distributed feedback lasers, the effect of incorporating wavelength-scale microstructure on the output of the devices is examined along with the ability to create such structures using simplified fabrication processes such as soft lithography. Conjugated materials have received a great deal of interest due to their broad spectral absorption, emission, ability to exhibit gain and ease of processing from solution. As a result, they show great potential for a variety of applications such as photovoltaics, displays, amplifiers and lasers. To date however, there has only been one demonstration of a polymer optical amplifier. A broadband, solution based polymer amplifier is presented where the gain overlaps with the transmission window of polymer optical fibres. The effect of transitions that reduce the availability of gain in conjugated polymers is also examined by studying saturation of absorption in thin films. Producing wavelength scale microstructure is traditionally a slow, expensive technique. Here, solvent assisted micromoulding is used to pattern polymer films in less than two minutes. The effect of the variations in the pattern transfer on the laser characteristics is examined. The micromoulding technique is then applied to fabricating novel device types such as circular gratings and flexible plastic lasers. Encapsulation of the micromoulded laser is then shown to improve the lifetime of the device by over three orders of magnitude. The degradation effects witnessed during this extended operation are characterised quantitatively, an area of study where little data exists in the literature. A novel class of branched dendrimer materials whose properties can be independently tuned due to their modular architecture are configured as blue-emitting distributed feedback lasers. The ability to tune the emission wavelength by varying the film thickness is demonstrated. By changing the chemical groups contained within the molecule, further tuning of the emission can be obtained along with the demonstration of a highly efficient blue-emitting dendrimer laser. Chemosensing using dendrimer lasers is presented by demonstrating the incredibly sensitive response of the laser device to trace vapours of nitro-benzene compounds. The future application of which could be highly beneficial in the detection of explosives.

Organic solar cells offer the possibility for lightweight, flexible, and inexpensive photovoltaic devices. This thesis studies the physics of a wide range of materials designed for use in organic solar cells. The materials investigated include conjugated polymers, conjugated dendrimers, and inorganic nanocrystals. The materials studied in this thesis fall into five categories: conjugated polymers blended with a buckminsterfullerene derivative PCBM, nanocrystals synthesised in a conjugated polymer matrix, conjugated polymers designed for intramolecular charge separation, conjugated dendrimers blended with PCBM, and nanocrystals synthesised in a matrix of conjugated small molecules or dendrimers. Conjugated polymers blended with PCBM have been extensively studied for photovoltaic applications, and hence form an ideal test bed for new experiments. In this thesis this blend was used to achieve the first pulsed electrically detected magnetic resonance experiments on organic solar cells. Nanocrystals are attractive for photovoltaics because it is possible to tune their band gap across the solar spectrum. In this thesis a one-pot synthesis is used to grow PbS and CdS nanocrystals in conjugated polymers, soluble small molecules, and dendrimers, and characterisation is performed on these composites. Previous work on dendrimer: nanocrystal composites has been limited to non-conjugated molecules, and the synthesis developed in this thesis extends this work to a conjugated oligomer and a conjugated dendrimer. This synthesis can potentially be extended to a variety of conjugated soluble small molecule: nanocrystal and dendrimer: nanocrystal systems. Conjugated dendrimers have been successfully employed in organic light emitting diodes, and in this thesis they are applied to organic solar cells. Materials based on fluorene and cyanine dye cores show excellent absorption tunability across the solar spectrum. A set of electronically asymetric polymers designed for intramolecular charge separation were investigated. Quenching of the luminescence was observed, and light induced electron paramagnetic resonance measurements revealed that photoexcitation led to approximately equal numbers of positive polarons and nitro centred radical anions. This indicates that charge separation is occurring in these molecules.

In the past decade, tremendous progress has been made in organic field effecttransistors. Fused oligothiophenes and anthracene molecules are fascinatingmacromolecules having unique optoelectronic properties. These compounds are successfully employed as active components in optoelectronic devices including field effect transistors. Our goal is to design and synthesize conjugated molecular materials, which are highly functionalized through structural modifications in order to enhance their electronic, photonic, and morphological properties. The main desire is to synthesize novel organic fused-arenes having efficient charge carrier mobilities, as well as to optimize optical properties for organic field effect transistors (OFETs). Novel series of fused arene molecules of 9,10-di(thiophen-3-yl)anthracene (1), trans-2,5-(dianthracene-9- vinyl)thiophene (2), trans-5,5’-(dianthracene-9-yl)vinyl)- 2,2’-bithiophene (3), 5,5’-di(2 thiophene)-2,2’-bithiophene (4) , 9,10-(divinyl)anthracene core with 1- phenylcarboxypyrene (6) and polymers of poly(anthracene-co-bithiophene) (5) and poly(anthracene) (7) have been synthesized as promising materials for organic field effect transistors (OFETs). These compounds were confirmed and characterized by 1H-NMR, FT-IR, and elemental analysis. Their optical, thermal, and electronic properties were investigated using UV-Vis and photoluminescence spectroscopy, and thermogravimetric analysis respectively. Future studies will focus on evaluating OFETs performance of these material.

A system packaging level approach on liquid crystal polymer (LCP) was proposed for low cost, lightweight, and compact wireless communication systems. Via technology was explored for V-band W-band transitions and an active cooling system that are essential for compact multilayer integration. RF MEMS switches were fabricated and integrated at the component level to enable multi-functional devices with optimal performance. A pattern reconfigurable antenna for MIMO applications and 3D phase shifters for phased array antennas that use RF MEMS switches were presented. In addition, a lightweight expandable array was designed and measured with up to 256 elements on multilayer LCP integrated at the system level. Furthermore, a 60 GHz multilayer transceiver front end device with simultaneous transmit and receive was designed and measured for low cost 60 GHz applications. The wide variety of multilayer LCP applications integrated at the system level shows a promising future for the next generation low cost lightweight wireless communication systems.

This thesis discusses the investigation and utilization of a new promising thin-film material, liquid crystal polymer (LCP), for microwave and millimeter-wave (mm-wave [>30 GHz]) components and packages. The contribution of this research is in the determination of LCP's electrical and mechanical properties as they pertain to use in radio frequency (RF) systems up to mm-wave frequencies, and in evaluating LCP as a low-cost substrate and packaging material alternative to the hermetic materials traditionally desired for microwave circuits at frequencies above a few gigahertz (GHz). A study of LCP's mm-wave material properties was performed. Resonant circuit structures were designed to find the dielectric constant and loss tangent from 2-110 GHz under both ambient and elevated temperature conditions. Several unique processes were developed for the realization of novel multilayer LCP-based RF circuits. These processes include thermocompression bonding with tight temperature control (within a few degrees Celsius), precise multilayer alignment and patterning, and LCP laser processing with three different types of lasers. A proof-of-concept design that resulted from this research was a dual-frequency dual-polarization antenna array operating at 14 and 35 GHz. Device characterization such as mechanical flexibility testing of antennas and seal testing of packages were also performed. A low-loss interconnect was developed for laser-machined system-level thin-film LCP packages. These packages were designed for and measured with both RF micro-electromechanical (MEM) switches and monolithic microwave integrated circuits (MMICs). These research findings have shown LCP to be a material with uniquely attractive properties/capabilities for vertically integrated, compact multilayer LCP circuits and modules.