Recently, atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) materials have drawn significant attention due to their unique optical and electrical properties1, 2. This offers unique opportunities for the next-generation electronic and optoelectronic devices3. Specifically, recent innovations in the big-data-driven prediction of new 2D materials, integration of new device architectures, interfacial engineering of contacts between semiconductor/metals and semiconductor/dielectrics as well as encapsulation in hexagonal boron nitride4, 5 have further propelled the electrical mobility to be on a par with or even beyond the silicon (Si) counterpart. These strategies hold tantalizing prospects on extending the Moore's law. Yet, there is still room for improvement before 2D TMDCs become truly technologically relevant. The challenge lies in the full validation of the intrinsic charge transport that is associated with the specific nature and ordered arrangement of atoms in the atomically thin crystal lattice. This requires, the controlled stitch of both metals and chalcogenides in an atom-by-atom fashion. To this end, a variety of synthetic approaches have been developed, this includes but not limited to chemical vapor deposition (CVD) 6, 7, mechanical exfoliation8 and solution-based exfoliation9. Among which, CVD shows better controllability over thicknesses, geometric shapes, sizes, and qualities through manipulation of the growth factors, e.g., growth temperature, pressure, precursor ratio, and gas carrier. These complex growth environments will significantly confound the scalability, crystallinity, defect density, and reproducibility of the CVD approach. Therefore, an impetus exists to gain fundamental insights into the universal growth mechanism that is currently lacking and therefore curbs the realization o the controlled epitaxy of high-mobility three-atom-thick semiconducting TMDCs films with wafer-scale-homogeneity. In this thesis, a mechanistic study toward revealing the epitaxy growth mechanism is established to include 1) epitaxy growth of multilayer, 2) epitaxy growth of heterostructures, and 3) epitaxy growth of high quality (exceedingly low defect density) of 2D TMDCs materials through a controlled CVD strategy.

Carbon nanotube forests (CNTFs) are grown using an injection chemical vapor deposition method. Images of CNTFs are taken using a scanning electron microscope and are used to measure their height and density. Growth parameters are systematically varied to determine their effect on the height and density of CNTFs. Investigations of CNTF density as a function of distance from the growth substrate reveal that diffusion can be a limiting factor on CNTF growth. Our findings indicate that height and density are related and that each growth parameter has multi-dimensional effects.

In this thesis,zirconium carbide (ZrC) layers were deposited on graphite substrates using a CVD reactor at temperatures ranging from 1250 °C to 1450 °C in steps of 50 °C. The deposited layers were characterised by XRD, Raman Spectroscopy and SEM.ZrCsamples were also prepared by spark plasma sintering (SPS), at 1700, 1900 and 2100 °C at 50 MPa for 10 minutes. The phase and microstructure after the sintering process were investigated by XRD and SEM. Iridium (Ir) thin films were deposited on these ZrCsamples and annealed in vacuum at temperatures of 600 and 800 °C for 2h. The phase composition, solid-state reactions and surface morphology were investigated by GIXRD and SEM. XRD was used to identify the phases present in the as-deposited and annealed samples. It showed that Ir2Zr was the initial phase formed at 600 °C. At temperature 800 °C IrZr formed. / Thesis (PhD (Physics))--University of Pretoria, 2019. / University of Pretoria / Physics / PhD (Physics) / Unrestricted

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Self assembled monolayers (SAMs) are widely used for surface modification. Alkylsilane monolayers are one of the most widely deposited and studied SAMs. My work focuses on the preparation, patterning, and application of alkysilane monolayers. 3-aminopropyltriethoxysilane (APTES) is one of the most popular silanes used to make active surfaces for surface modification. To possibly improve the surface physical properties and increase options for processing this material, I prepared and studied a series of amino silane surfaces on silicon/silicon dioxide from APTES and two other related silanes by chemical vapor deposition (CVD). I also explored CVD of 3-mercaptopropyltrimethoxysilane on silicon and quartz. Several deposition conditions were investigated. Results show that properties of silane monolayers are quite consistent under different conditions. For monolayer patterning, I developed a new and extremely rapid technique, which we termed laser activation modification of semiconductor surfaces or LAMSS. This method consists of wetting a semiconductor surface with a reactive compound and then firing a highly focused nanosecond pulse of laser light through the transparent liquid onto the surface. The high peak power of the pulse at the surface activates the surface so that it reacts with the liquid with which it is in contact. I also developed a new application for monolayer patterning. I built a technologically viable platform for producing protein arrays on silicon that appears to meet all requirements for industrial application including automation, low cost, and high throughput. This method used microlens array (MA) patterning with a laser to pattern the surface, which was followed by protein deposition. Stencil lithography is a good patterning technique compatible with monolayer modification. Here, I added a new patterning method and accordingly present a simple, straightforward procedure for patterning silicon based on plasma oxidation through a stencil mask. We termed this method subsurface oxidation for micropatterning silicon (SOMS).

A modified CVD reactor was designed with a deposition chamber capable of accommodating 8" wafers, with the capacity to remotely pyrolyze two different precursors. The design was based on a previous working reactor, with the most notable improvements being a showerhead design for more even delivery of gaseous precursor and a separate heating control of the substrate holder and deposition chamber walls. The performance of the reactor was analyzed by testing the pressure gradients within and the thickness uniformity of films deposited on 8" wafers. The reactor exhibited a linear pressure gradient within, and the thickness uniformity was excellent, with a slight increase in thickness towards inlet of the showerhead. The thickness difference between the maximum and minimum thickness on an 8" wafer was 14%. Films of polyparaxylylene (PPXN), polychloroparaxylylene (PPXC), SiO₂, and PPXC/SiO₂ were deposited, with deposition rates and indices of refraction comparable to those obtained on the old reactor design. A full factorial study was performed to determine the effect of the substrate temperature, the sublimation temperature, and the pyrolysis temperature on the deposition rates of PPXC. It was determined that the substrate temperature has the greatest effect, with about 50% contribution, and deposition rates increased with decreasing substrate temperature. The sublimation temperature contributed 25%, with increasing sublimation rates leading to higher deposition rates. The pyrolysis contributes very little, with about 2%, and the variance ratio did not fall within a 90% confidence level. A low dielectric constant polymer, poly(tetrafluoro-p-xylylene) (VT-4), was synthesized by chemical vapor deposition from 4,5,7,8,12,13,15,16-octafluoro-[2.2]-paracyclophane (DVT-4). The main motivation was to find a cheaper alternative to poly( alpha, alpha , alpha ', alpha '-tetrafluoro-p-xylylene) (AF-4) with similar properties. The dielectric constant of VT-4 was measured as 2.42 at 1 MHz, and the in-plane and out-of-plane indices of refraction were 1.61 and 1.47 at 630 nm. The large negative birefringence suggests a low out-of-plane dielectric constant, which is desired for interlayer dielectrics. The VT-4 polymer was found to be stable at 460 °C by thermogravimetric analysis (TGA). Polymer/Siloxane nanocomposites were studied as an alternate path to a polymer/silica composite. This study showed that incorporation of a four-ringed liquid siloxane precursor into the parylene PPXC is not feasible. A solid precursor cube-like molecule, vinyl-T8, was incorporated with ease. Pyrolysis of vinyl-T8 at different temperatures revealed complex behavior, with the formation of polymerized vinyl-T8 (through free radical addition at the vinyl groups) as well as silica-like structures forming above 500 °C as a result of the breaking up of the cage structure of vinyl-T8. Codepositions of PPXC and vinyl-T8 were then examined as a possible path towards a polymer/silica nanocomposite. At deposition temperatures below 5 °C, precipitation of excess vinyl-T8 into cubic micron-sized crystals occurred. As this was undesirable, studies were continued at higher deposition temperatures. A Taguchi orthogonal array was set up to study the effect of the sublimation temperatures of the two precursors as well as the pyrolysis temperature and the substrate temperature on the deposition rate, the index of refraction and the weight loss after a 500 °C anneal. The deposition rate depended mostly on the sublimation temperature of the PPXC and the substrate temperature. The lowest index of refraction (and thus the lowest dielectric constant) was obtained with the lowest sublimation temperatures of 134 °C for PPXC and 195 °C for vinyl-T8 and a pyrolysis temperature of 200 °C. Each of the factors was found to have an effect on the index of refraction, with the sublimation temperature of vinyl-T8 having the most influence. The films degraded at 500 °C, indicating that post-deposition annealing of the films did not lead to a conversion of the vinyl-T8 to a SiO₂-like structure (which would be stable at that temperature). X-ray diffraction spectra of the films revealed peaks which were not present for any of the vinyl-T8 films or characteristic of PPXC. Therefore, some type of interaction between the two components occurred and affected the morphology, most likely the formation of a block copolymer. Thus, though polymer/silica films were not attained, the resulting composites had comparable properties with higher deposition rates and a cleaner process. / Master of Science

Information processing is crucial in modern society, placing a great emphasis on the performance of optoelectronic devices to match ever increasing processing and memory needs. Within these devices, MoS2 has demonstrated great potential as transistors due to its enhanced electrostatic control. As increased layer thickness of quality MoS2 films have been shown to boost the performance of its transistors, growth parameters for the synthesis of ideally uniform and large area multilayered films via chemical vapor deposition were investigated. By increasing the flow pressure in the system and the growth time, increasing levels of thickness and nucleation density was shown for MoS2 growth. Although the scale of the growth was non-uniform in nature, films containing large areas of thicker MoS2 was achieved. The thickness of the films was confirmed by Raman and photoluminescence measurements by confirming their values with exfoliated MoS2 measurements.

With the low-temperature halo-carbon epitaxial growth technique developed at MSU prior to this work, use of a halo-carbon growth precursor enabled low-temperature homoepitaxial process for 4H-SiC at temperatures below 1300 °C with good quality. Investigations of the nitrogen doping dependence are reported. It has been demonstrated that the efficiency of the nitrogen incorporation may be different for different substrate orientations, with the Cace showing the higher value of doping. The Si/C ratio is known to influence the doping during the epitaxial growth due to the site-competition mechanism. The doping on the Cace showed weak dependence on the Si/C ratio. On the Siace, the doping dependence follows the site-competition trend. At high Si/C ratio, the doping trend on Siace shows strong deviation. Both of the investigated trends are suggested for use as the main process dependencies for achieving a wide range of n type doping of SiC during the low-temperature halo-carbon homoepitaxial process.

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No description available.