A simple, low cost microwave plasma enhanced chemical vapour deposition (PECVD) technique for the production of carbon nanostructures has been developed in the School‟s Materials Science Laboratory. The technique utilises a conventional microwave oven as an energy source, various hydrocarbons as a carbon source, a metallic aerial as a catalyst and hydrogen to support the process. The input hydrocarbon and the hydrogen flow rate are independently varied to investigate their effect on the resultant nanostructures. This technique allows for the production of carbon nanotubes (CNTs), onion-like nanostructures structures (ONSs) and amorphous carbon, which has been verified via transmission and scanning electron microscopy. A change in input parameters results in the controllable yield of CNTs versus ONSs. The formation of amorphous carbon is reduced by controlling the hydrogen flow rate. In further experiments, the thermal conductivity of the ONSs is investigated using the "Lee‟s Disk" method. It was observed that bulk ONS specimens exhibit a thermal conductivity above that of amorphous carbon powder. Insufficient quantities of CNTs were grown using this method to facilitate a comparable thermal conductivity investigation. / Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2010.

Thesis (Ph.D.)--University of Wollongong, 2005. / Typescript. Includes bibliographical references: leaf 191-198.

Strongly correlated oxides are studied widely for the host of unique applications, such as hightemperature superconductivity, colossal magneto resistance, exotic magnetic, charge and orbital ordering, and insulator-to-metal transitions. Transitional metal oxides which form the majority of the correlated oxide systems and oxides of Vanadium, especially VO2 and V2O5 are the two most favourite systems among researchers for several applications. In this thesis, the growth and characterization of VO2 and V2O5 are discussed along with a special focus on the optical property, especially thermochromic properties. Traditionally SMT behaviour and Infrared reflectively was the focus area for VO2 research, and its only until recently that VO2 is being treated as a much more complex system and investigated as highly responsive naturally disordered metamaterial near the phase transition temperature where the material exhibits semiconducting and metallic phase co-existence. Since each phase of VO2 has a distinct optical and electrical properties, controlling the extent of phase transitions by accurate temperature modulation, enables exploitation of the material for new properties like emissivity modulation in the NIR region and for creating IR visible reversible and rewritable patterns. V2O5 is traditionally seen as a high TCR material and regarded as material of choice for application ranging from catalysis, gas sensors to lithium batteries. In this study, however we focus on the optical properties of the material, especially the visible range thermochromic nature of V2O5 coatings synthesised by oxidative annealing of MOCVD grown VOx coatings. The impact of doping and selective oxygen vacancy generation on the thermochromic property are discussed

>Magister Scientiae - MSc / Perovskite solar cells have gained tremendous attention within the past decade, due to its rapid improvement in power conversion e ciency (PCE), with the current record cell at 25%. The aim of this study is to create a repeatable and scalable chemical vapour deposition technique that can be used to construct perovskite solar cells with a high PCE while maintaining long-term stability. The technique requires the formation of a uniform and compact lead halide layer, either PbI2 or PbCl2 that is sequentially converted into the perovskite structure with the exposure of Methylammonium iodide (MAI) vapour. The use of CVD with a 5 cm diameter quartz tube was successfully used to deposit uniform thin lms of both PbI2 and PbCl2 over an area of 6 cm2 with a thickness deviation of 5%. Thickness control was obtained by varying the amount of source material which allows for repeatable control within 5% error, without the need for a crystal thickness monitor.

Increase in demand for uniform ceramic coatings on larger industrial components have led to a need for a PP-MOCVD coating system scale up. The objective of this thesis is to develop a fully functional coating system operating in the PP-MOCVD regime that is able to deposit thin film ceramic coatings on commercial or industrial components with complex 3D geometries. This can be achieved by applying engineering and vacuum science theories, coupled with the established fundamentals of PP-MOCVD. A larger system was designed and assembled around the boundaries set by the dimensions and geometry of a stainless steel water pump impellor acting as the base substrate. Most of the components were sourced off the shelf from vacuum and fluid specialists. Components which were unavailable for various reasons were designed, and machined in-house by the departmental workshop. Initial test depositions were conducted using small stainless steel disk substrates, heated using a resistive heater similar to the one utilised on the research scale system. The test depositions were performed with the heater and substrate combination placed in strategic locations. This is to test the overall uniformity of precursor flux in the chamber volume. The resulting coating uniformity on the disk surfaces were fair but problems such as the large collection of unreacted precursor on the chamber viewport and valve timing issues had to be addressed. Before making any improvements to the system, each of the process areas leading to a successful deposition needed to be understood. Five process areas were developed: ‘Liquid Delivery’, ‘Atomization’, ‘Evaporation’, ‘Transport and Reactor Geometry’, and ‘Droplet Management’. Each of the process areas were analysed individually and changes were made to push for a maximum evaporation efficiency. xviii The improved system provided opportunities to perform depositions that were once not possible for PP-MOCVD. Two sets of deposition tests were designed and conducted. Firstly, the improvements were justified with a series of depositions using flat stainless steel plates with dimensions 65x65x5mm. The other set of 3D case study depositions involve observing the effects of the operational parameters of PP-MOCVD on the uniformity and penetration depths of the coatings into different sized macro blind trenches. Five geometric setup conditions were used to justify the improvements made to the system. These are: ‘Substrate positioned in the direct line of spray’, ‘Use of an unheated receptor’, ‘Use of a heated receptor’, ‘Use of an unheated receptor with a non-axial substrate setup’, and “Choked Flow’. As expected, the uniformity of the coatings on both sides of the plate varied significantly when the substrate is placed over the line of sight of the precursor spray. Similarly, the coating produced under the induced choked flow condition resulted in low conformality. The introduction of an unheated receptor plate resulted in an increase in uniformity on both sides of the plate. Further prove that PP-MOCVD is geometry independent is provided by the deposition made with the non-axial substrate placement resulting in a coating of similar result to the unheated receptor. The use of a heated receptor provided a source for a secondary evaporation of the larger precursor droplets collected resulting in an increase in coating thickness while maintaining good conformality. The effects of temperature, pressure, injection volume, and concentration were explored in the final case study. With maximum depths of 50mm, the macro blind trenches has an aspect ratio of 1:1 and cross-sectional areas of 3x3mm, 9x9mm, and 15x15mm. The final results show that as the temperature rises, the depth penetrated into the trench decreases. This could be due to the change in rate limiting steps as homogeneous reactions begin to increase at higher temperatures. Similar trends were observed with increasing pressure. As the pressure difference between the volume of the trenches and the rest of the chamber decreases, the push needed to xix force the precursor down the trench also decreases, resulting in less depth penetration. The effects of injection volume and concentration observed, can be explained by how much precursor molecules are present during one pulse cycle. The more that is available at any given time, the more likely a reaction will occur and deeper the penetration will get. Of course a ceiling or a limit exists where the molecules in the chamber will get evacuated without being reacted. The future work made possible as a result of the scaled up system are proposed. These include a scale up of the operational parameters to suit any given substrate geometry, improvements to the heating source to achieve greater thermal uniformity, further improvements to the overall system accessibility, and performing other depositions using different substrate materials and precursor types.

This work mainly investigates the use of aerosol assisted chemical vapour deposition (AACVD) process to fabricate thin film materials for energy efficient glazing and thin film solar cells applications. Ga-doped ZnO thin films were firstly deposited onto glass substrates by AACVD of zinc and gallium acetylacetonates in methanol. After optimizing the doping concentration, film thickness and heating temperature, ZnO:Ga coatings with high visible transparency (> 80 %) and infrared reflection (up to 48.9 % at 2500 nm) were obtained, which is close to the optical requirements for commercial energy saving glazing. Pyramid-shaped and plate-shaped zinc oxides films were then deposited on glass substrates by AACVD of zinc-acetate-dihydrate, acetic acid and deionized water in methanol. These surface-textured ZnO films exhibited good visible transparency (~70 %), low sheet resistance (~60 Ω sq-1) and ultra large haze factor (up to 98.5 %), which is the most hazy ZnO ever reported and can be potentially used as the front contact in thin-film solar cells. Finally, uniform compact CH3NH3PbI3 perovskite films with high phase purity and micron-sized pinhole-free grains were deposited on glass substrates by a novel two-step and three-step sequential AACVD process. In conclusion, AACVD shows a great potential for the scalable fabrication of ZnO-based and organometallic halide-based thin film materials.

This work investigates the use of the novel electric field assisted chemical vapour deposition (EACVD) process in the production of titanium dioxide thin films for photocatalytic applications on glass substrate. This work looks into the interaction of applied electric fields with the precursor species during the aerosol assisted chemical vapour deposition (AACVD) and atmospheric pressure chemical vapour deposition (APCVD) reaction of Titanium isopropoxide (TTIP) and Titanium (IV) Chloride (TiCl4) with different solvents. The electric field was generated by applying a potential difference between two fluorine-doped tin oxide glass sheets. The electric field was varied between 0 – 3000 Vm-1. The deposited films were analysed and characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, atomic force microscopy, UV-vis spectroscopy, water-contact angles and resazurin photcatalytic testing. It was observed that the application of electric fields produced changes in the morphology, particle size, growth rate, crystal orientation and crystal phases. Generally, films produced under the influence of the electric fields showed higher photo-activity than films produced in absence of electric fields. The deposited films produced from the electric field assisted aerosol chemical vapour deposition (EAACVD) showed higher photo-activity with applied AC electric fields than with applied DC electric fields. Likewise, they showed higher photo-activity than the deposited films produced from the electric field assisted atmospheric pressure chemical vapour deposition (EAAPCVD) with applied AC electric fields. The results obtained were explained by the interaction mechanisms between the electric fields and the precursor species, which differ depending on the CVD technique used. Although titanium dioxide photo-activity is comprised by a combination of factors, it was observed that an optimum can be obtained by varying both experimental conditions and field strength. In particular, optimum results were obtained for deposited films which showed long-shaped particles, reduced particle size and high preferential orientation in the anatase (004) plane. Electric field assisted chemical vapour deposition (EACVD) shows a great potential for the improvement of commercial products available in the market such as self-cleaning and antibacterial surfaces.

The production of large area, high quality two-dimensional (2D) materials using chemical vapour deposition (CVD) has been an important and difficult topic in contemporary materials science research, after the discovery of the diverse and extraordinary properties exhibited by these materials. This thesis mainly focuses on the CVD synthesis of two 2D materials; bilayer graphene and monolayer tungsten disulphide (WS2). Various factors influencing the growth of each material were studied in order to understand how they affect the quality, uniformity, and size of the 2D films produced. Following this, these materials were combined to fabricate 2D vertical heterostructures, which were then spectroscopically examined and characterised. By conducting ambient pressure CVD growth with a flat support, it was found that high uniform bilayer graphene could be grown on the centimetre scale. The flat support provides for the consistent delivery of precursor to the copper catalyst for graphene growth. These results provide important insights not only into the upscaling of CVD methods for growing large area, high quality graphene and but also in how to transfer the product onto flexible substrates for potential applications as a transparent conducting electrode. Monolayer WS2 is of interest for use in optoelectronic devices due to its direct bandgap and high photoluminescence (PL) intensity. This thesis shows how the controlled addition of hydrogen into the CVD growth of WS2 can lead to separately distributed domains or centimetre scale continuous monolayer films at ambient pressure without the need for seed molecules, specially prepared substrates or low pressure vacuum systems. This CVD reaction is simple and efficient, ideal for mass-production of large area monolayer WS2. Subsequent studies showed that hexagonal domains of monolayer WS2 can have discrete segmentation in their PL emission intensity, forming symmetric patterns with alternating bright and dark regions. Analysis of the PL spectra shows differences in the exciton to trion ratio, indicating variations in the exciton recombination dynamics. These results provide important insights into the spatially varying properties of these CVD-grown TMDs materials, which may be important for their effective implementation in fast photo sensors and optical switches. Finally, by introducing a novel non-aqueous transfer method, it was possible to create vertical stacks of mixed 2D layers containing a strained monolayer of WS2, boron nitride, and graphene. Stronger interactions between WS2 on graphene was found when swapping water for IPA, likely resulting from reduced contamination between the layers associated with aqueous impurities. This transfer method is suitable for layer by layer control of 2D material vertical stacks and is shown to be possible for all CVD grown samples, a result which opens up pathways for the rapid large scale fabrication of vertical heterostructure systems with large area coverage and controllable thickness on the atomic level.

Diamond is an important material in many industrial applications (e.g., machining of hard materials, bio-electronics, optics, electronics, etc.) because of its exceptional properties such as hardness, tolerance to aggressive environments, compatibility with human tissues, and high carrier mobility. However, a highly controlled method for growing artificial high-purity diamond on a range of different substrates is needed to exploit these exceptional properties. The Chemical Vapour Deposition (CVD) method is a useful tool for this purpose, but the process still needs to be developed further to achieve better control of growth. In this context, the introduction of dopant species into the gas phase has been shown to strongly influence growth rate and surface morphology. Density Functional Theory (DFT) methods are used to deepen our atomic-level understanding of the effect of dopants on the mechanism for CVD growth on diamond. More specifically, the effect of four dopants (N, P, B and S) has been studied on the important reaction steps in the growth mechanism of diamond. Substitution of N into the diamond lattice has generally been found to disfavour critical reaction steps in the growth of the 100-face in diamond. This negative effect has been related to electron transfer from the N dopant into an empty surface state, e.g., a surface carbon radical. In addition, strong surface stabilization is observed for N substitution in certain sites via a beta-scission reconstruction, with the formation of sp2 carbon. These observations correlate well with observed surface degradation and decrease in growth rate when a high concentration of nitrogen gas is introduced into the CVD growth process. The effect of co-adsorbed P, S and B onto the diamond surface has also been investigated for two reaction steps: CH3 adsorption and H abstraction. While P and B are observed to influence these reaction steps, the effect of S is rather limited.

Carbon nanostructures are a wide field with many applications. The use of carbon nanostructures as support in heterogeneous catalysis is a key development that led together with the use of nanoparticles to a significant cost reduction of catalysts. Catalysts designed in this way are widely applied in fuel cell technologies. For portable devices especially low temperature fuel cells are desirable with low hazards for the user. One technology which fulfills these requirements is the direct formic acid fuel cell (DFAFC). DFAFC have many promising characteristics, such as high electromotive force and easy fuel handling. However, they still suffer from too low power output and lifetime for commercialization. This thesis focusses on two main aspects: the synthesis of carbon nanostructures by chemical vapor deposition (CVD) and their application as catalyst support. The materials are investigated by many different techniques ranging from transmission electron microscopy (TEM) to fuel cell tests. Different carbon nanostructures could be synthesized by catalytic CVD on palladium (Pd) nanoparticles. Multi-walled carbon nanotubes (MWCNTs), carbon nanofibers (CNFs) and helical carbon nanofibers (HCNFs) were grown, selectively, dependent on temperature, using acetylene as carbon precursor. Especially HCNF raised further interest due to their unique structure. A growth model for HCNFs was developed based on an anisotropic extrusion model. The synthesis conditions for HCNFs were optimized until an almost 100 % purity with very high efficiency was obtained. The unique helical but fiber-like structure made the material very interesting as support for heterogeneous catalysis. Several catalysts based on Pd nanoparticle decorated HCNFs were developed. The synthesis methods ranged from standard methods like the polyol method to phase-transfer methods. The catalysts showed very promising results for the electro-oxidation of methanol, ethanol and formic acid. This makes them highly attractive for fuel cell applications. The catalysts were tested in DFAFC. The superiority of HCNF-based catalysts is attributed to the good attachment of nanoparticles to the defect-rich and easy to functionalize surface of HCNFs in combination with adequate film forming properties during electrode preparation. / Nanostrukturerat kol är ett mycket brett fält med ett stort antal tillämpningar. Användning av kolnanostrukturer som support för heterogena katalysmaterial har tillsammans med utvecklingen av nanopartiklar lett till en avsevärd minskning av kostnaden för katalysatorer. Katalysatorer designade på detta sätt används frekvent i bränsleceller. För portabla tillämpningar är utvecklingen av säkra och miljövänliga lågtemperaturceller mycket viktig. En teknologi som uppfyller dessa kriterier är bränsleceller som drivs med myrsyra (DFAFC). Sådana bränsleceller har många önskvärda egenskaper, såsom en hög elektromotorisk kraft och en enkel hantering av bränslet. Trots dessa goda egenskaper har de också en del nackdelar som hindrar en full kommersialisering. De två mest problematiska är en för låg genererad effekt samt en för kort livslängd på katalysatorerna. Denna avhandling fokuserar på två huvudpunkter som adresserar dessa problem; tillverkning och karaktärisering av kolnanostrukturer producerade med CVD, och deras tillämpningar som support för katalysatorer. Materialen karaktäriseras med en rad olika tekniker, allt från transmission-elektronmikroskopi till bränslecellstester. Olika kolnanostrukturer har syntetiserats med katalytisk CVD på palladium (Pd) nanopartiklar. Produktionen av flerväggiga kolnanorör, kolfibrer och heliska kolnanofibrer har tillverkats med acetylen som kolkälla och genom att variera temperaturen kunde innehållet av olika typer av nanostrukturerat kol kontrolleras. Särskilt stort intresse har de heliska kolnanofibrerna rönt på grund av deras unika struktur. Vi beskriver en tillväxtmekanism baserad på en anisotrop diffusionsmodell. Genom att justera produktionsparametrarna visar vi att heliska kolnanofibrer kunde tillverkas med nära 100 %-ig renhet och hög effektivitet. Den unika heliska och fiberlika strukturen är mycket intressant for tillämpningar som support för heterogena katalysatorer. Ett flertal kompositer för katalytiska tillämpningar har utvecklats baserade på heliska kolnanofibrer, dekorerade med heterogena katalysatorer genom en rad olika kemiska/fysikaliska tekniker. De syntetiserade materialen visar mycket goda katalytiska egenskaper för att oxidera metanol, etanol och myrsyra. Därigenom blir de mycket attraktiva för användning i bränsleceller. Vi korrelerar de goda katalytiska egenskaperna med en bra vidhäftning av nanopartiklarna på de heliska kolnanofibrerna defekter, deras goda ledningsförmåga, bra egenskaper för att förbereda elektroder, samt deras stora yta i förhållande till deras volym och vikt.