Pyrite (FeS2) has recently attracted significant interest as a photovoltaic material due to its promising optical properties, high photon to electron conversion yield, and low-cost raw materials. However, hopes have been tempered by recent discoveries that suggest the presence of hard to remove bulk sulfur defects. This research was focused on engineering and implementing the crystallization of pyrite from a sulfur rich solution to counteract the material's natural tendency to form bulk sulfur defects. Homoeptiaxial layers and single-crystal samples have been grown from tellurium sulfur melts with an Fe:S ratio of 1:4 using both natural and synthetic substrates. The homoepitaxial layer has been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM), confirming the epitaxial nature of the synthetic FeS2 layer, and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) to better understand the energetics of the grown materials. Furthermore, epitaxial growth onto natural pyrite, in contrast to substrate etching, was established using sulfur-34 substitution and secondary ion mass spectrometry (SIMS). Growth onto synthetic pyrite was also described. Finally, the photovoltaic properties of homoepitaxial layers of high temperature solution growth pyrite onto a synthetic templating crystal was characterized using electrochemical methods.

The wide band-gap semiconductor silicon carbide has tremendous potential for use in high power, high temperature, and high frequency electronic devices. One of the more important design factors for these devices is the epitaxial layer. It is desirable that this thin film have uniform polytype, thickness, and impurity concentration, as well as be defect free. One method used for SiC to ensure epitaxial layers with homogenous polytype is to cut wafers from a boule that has been tilted towards a specific crystallographic face at a fixed angle (known as ?off cut?). The purpose of this thesis was to investigate the growth mechanisms of alternative boule tilting directions with 6H-SiC. Four alternative crystallographic tilting faces were chosen: <1230>, <1340>, <2130>, and <3140>. A lightly doped 1um-thick layer was grown on samples representing the four alternative off-cut directions and, as references, commercially available substrates off cut towards the traditional direction <1120>. The physical and electrical properties of the layers were characterized by means of optical microscopy, Fourier Transform Infrared Reflectance Spectroscopy, Atomic Force Microscopy, capacitance vs. voltage, and current vs. voltage. Three facts were observed: 1) the alternative off-cut directions affected the growth mechanisms and surface morphology, 2) the quality of the substrate affects the morphology of the epitaxy layer, and 3) the relative differences between the surface roughness attributed to the different off-cut directions affected the observed electrical characteristics of Schottky barrier diodes fabricated on the epi layers. The samples cut towards the <31-40> and <13-40> directions showed to the most promising alternative off-axis tilting direction.

Thesis (Ph. D.)--University of Alabama at Birmingham, 2009. / Title from PDF title page (viewed Jan. 28, 2010). Additional advisors: Shane A. Catledge, Joseph G. Harrison, Raymond G. Thompson, Uday K. Vaidya. Includes bibliographical references (p. 75-78).

Master of Science / Department of Chemical Engineering / James H. Edgar / 4H-silicon carbide (4H-SiC) is a wide band gap semiconductor with outstanding capabilities for high temperature, high power, and high frequency electronic device applications. Advances in its processing technology have resulted in large micropipe-free single crystals and high speed epitaxial growth on off-axis silicon face substrates. Extraordinarily high growth rates of high quality epitaxial films (>100 [Mu]m per hour) have been achieved, but only on off-axis substrates (misoriented 4° to 8° from the (0001) crystallographic plane). There is a strong incentive to procure an on-axis growth procedure, due to the excessive waste of high quality single crystal associated with wafering off-axis substrates. The purpose of this research was to develop a reliable process for homoepitaxial growth of 4H-SiC on on-axis 4H-SiC. Typically the use of on-axis SiC for epitaxial growth is undesired due to the increased probability of 3C-SiC inclusions and polycrystalline growth. However, it is believed that the presence of chlorine during reaction may reduce the presence of 3C-SiC and improve the quality of the epitaxial film. Therefore homoepitaxial SiC was deposited using methyltrichlorosilane (MTS) and ethane sources with carrier gases consisting of argon-hydrogen mixtures. Ethane was used to increase the C/Si ratio, to aid in the prevention of 3C-SiC, and to help eliminate silicon droplets deposited during epitaxial growth. Deposition occurred in a homemade, quartz, cold wall chemical vapor deposition reactor. Epitaxial films on on-axis 4H-SiC were deposited without the presence of 3C-SiC inclusions or polycrystalline SiC, as observed by defect selective etching, scanning electron microscopy and optical microscopy. Large defect free areas, [similar to]5 mm[superscript]2, with epitaxial film thicknesses of [similar to]6 [Mu]m were grown on on-axis 4H-SiC. Epitaxial films had approximately an 80%, [similar to]20 cm[superscript]-2, decrease in defect density as compared to the substrates. The growth rate was independent of face polarity and orientation of the substrate. The optimal temperature for hydrogen etching, to promote the smoothest epitaxial films for on-axis substrates (both C- and Si-polarities), is [similar to]1550 °C for 10 minutes in the presence of 2 slm hydrogen. The optimum C/Si ratio for epitaxial growth on on-axis 4H-SiC is 1; excess carbon resulted in the codeposition of graphite and cone-shaped silicon carbide defects.

Wide band gap semiconductors such as MgxZn1-xO represent an excellent choice for making optical photodetectors and emitters operating in the UV spectral region. High crystal and optical quality MgxZn1-xO thin films were grown epitaxially on c-plane sapphire substrates by plasma-assisted Molecular Beam Epitaxy. ZnO thin films with high crystalline quality, low defect and dislocation densities, and sub-nanometer surface roughness were achieved by applying a low temperature nucleation layer. The critical growth conditions were discussed to obtain a high quality film: the sequence of Zn and O sources for initial growth of nucleation layer, growth temperatures for both ZnO nucleation and growth layers, and Zn/O ratio. By tuning Mg/Zn flux ratio, wurtzite MgxZn1-xO thin films with Mg composition as high as x=0.46 were obtained without phase segregation. The steep optical absorption edges were shown with a cut-off wavelength as short as 278nm, indicating of suitability of such material for solar blind photo detectors. Consequently, Metal-Semiconductor-Metal photoconductive and Schottky barrier devices with interdigital electrode geometry and active surface area of 1 mm2 were fabricated and characterized. Photoconductor based on showed ~100 A/W peak responsivity at wavelength of ~260nm. ZnO homoepitaxial growth was also demonstrated which has the potential to achieve very low dislocation densities and high efficiency LEDs. Two types of Zn-polar ZnO substrates were chosen in this study: one with 0.5° miscut angle toward the [1-100] direction and the other iv without any miscut angle. We have demonstrated high quality films on both substrates with a low growth temperature (610°C) compared to most of other reported work on homoepitaxial growth. An atomically flat surface with one or two monolayer step height along the [0001] direction was achieved. By detail discussions about several impact factors for the epitaxial films, ZnO films with high crystallinity verified by XRD in different crystal orientations, high PL lifetime (~0.35 ns), and not obvious threading dislocations were achieved. Due to the difficulty of conventional p-type doping with p dopant, we have explored the possibility of p-type doping with the assistance of other novel method, i.e. polarization induced effect. The idea is the sheet layer of two dimensional hole gases (2DHG) caused by the wurtzite structure’s intrinsic polarization effect can be expanded to three dimension hole distribution by growing a MgZnO layer with a Mg concentration gradient. By simulation of LED structure with gradient MgZnO structure, the polarization effect was found not intense as that for III-nitrides because the difference of spontaneous polarization between ZnO and MgO is smaller than that of GaN and AlN, and the piezoelectric polarization effect may even cancel the spontaneous polarization induced effect. We have grown the linear gradient MgZnO structure with Mg composition grading from 0% to 43%, confirmed by SIMS. Hall measurement did not show any p-type conductivity, which further indicates MgZnO’s weak polarization doping effect. However, the gradient MgZnO layer could act as an electron blocking layer without blocking holes injected from p layer, which is useful for high efficiency light emitters.