Defect structures and growth mechanisms of boron arsenide epilayers grown on 6H-silicon carbide and 15R-silicon carbide substrates

B12As2 possesses the extraordinary properties, such as wide bandgap of 3.47eV and unique 'self heal' ability from electron irradiation damage, which make it attractive for the applications in space electronics, high temperature semiconductors and in particular, beta cells, devices capable of producing electrical energy by coupling a radioactive beta emitter to a semiconductor junction. Due to the absence of native substrates, B12As2 has been grown on substrates with compatible structural parameters via chemical vapor deposition. To date, growth on Si with (100), (110) and (111) orientation and (0001) 6H-SiC has been attempted. However, structural variants, including rotational and translational variants, have been observed in the epilayers and are expected to have a detrimental effect on device performance which has severely hindered progress of this material to date. In addition, none of the earlier reports provide a detailed atomic level study of defect structures in the films and growth mechanisms remain obscure. The focus of this thesis is to study defect structures in B12As2 films grown on different SiC substrates using synchrotron x-ray topography, high resolution transmission microscopy as well as other characterization techniques. The goals of the studies are to understand the generations of the defects present in B12As 2 films and their growth mechanisms so as to develop strategies to reduce defect densities and obtain better film quality for future device fabrication. The following detailed studies have been carried out: (1) The microstructures in B12As2 epitaxial layers grown on on-axis c-plane (0001) 6H-SiC substrates were analyzed in detail. Synchrotron white beam X-ray topography (SWBXT) and scanning electron microscopy (SEM) revealed a mosaic structure consisting of a solid solution of twin and matrix epilayer domains. The epitaxial relationship was determined to be (0001)B12As2<112¯0> B12As2||(0001)6H-SiC<112¯0>6H-SiC. B 12As2 twinned domains were found in the epilayer and the twin relationship consisted of a 180° rotation about [0001]B12As2 . High resolution transmission electron microscopy (HRTEM) observation revealed an evolution of the film microstructure from an ∼200nm thick disordered mosaic transition layer to a more ordered structure. Observing the structural projections of the film lower surface and the substrate upper surface, generated by CaRine 4.0 crystal visualization software, eight possible nucleation sites were found to be available on the substrate surface by considering the stable bonding configurations between the boron triangles at the bottom of the boron icosahedra, and the Si dangling bonds on the Si oriented (0001) 6H-SiC substrate surface. The transition layer was suggested to arise from the coalescence of translationally and rotationally variant domains nucleated at the various nucleation sites on the (0001) 6H-SiC surface. Boundaries between translationally variant domains were shown to have unfavorable high-energy bonding configurations while the formation of a 1/3[0001]B12As2 Frank partial dislocation enabled elimination of these high energy boundaries during mutual overgrowth. In consequence, the film quality beyond thicknesses of ∼200nm can be improved as the translational variants grow out leaving only the twin variants. (0003) twin boundaries in the regions beyond 200nm are shown to possess fault vectors such as 1/6[11¯00]B12As2 which originates from the mutual shift between the nucleation sites of the respective domains. (2) The effect off-cut angle on substrate surface on the growth of B12As2 epitaxial layer was studied using a 3.5° off-cut (0001) 6H-SiC substrate. A combined characterized technique composed of SWBXT, SEM, conventional and HRTEM was employed. Similar to the growth on on-axis c-plane 6H-SiC, the epitaxial relationship is identified to be (0001)B12As2<112¯0>B12As2||(0001) 6H-SiC<1120>6H-SiC. It is also revealed that the epilayer consists of a solid solution of B12As2 twinned domains. The 3.5° off-cut angle breaks the surface symmetry of c-plane 6H-SiC, however, the width of each single terrace is large enough to provide eight possible nonequivalent nucleation sites for the growth of B12As 2. In consequence, there could be eight possible structural variants in the film which indicates that the 3.5° offcut angle has little effect in the reduction of possible structural variants in the epilayer and thus may not be an excellent substrate to grow high quality B12As 2 film. (3) Investigation of the microstructures of B12As 2 epitaxial layers grown on m-plane 6H-SiC substrates has been studied. A mosaic structure formed by six types of domains, including (1-21) B 12As2, (2-12) B12As2, (353) B 12As2 and their respective {111} twins, was found in the epilayer. The choice of the various growth orientations in the B12As 2 film were proposed to arise from the following factors: (1) the tendency for B12As2 to grow with {1-21} low energy surface facets; (2) the tendency to minimize the in-plane lattice mismatch between B 12As2 planes oriented approximately parallel to the SiC (0001) planes so as to alleviate local strain in the film/substrate interface; (3) the tendency to nucleate on 3-3 symmetric closed-packed atomic steps exposed on the substrate surface after hydrogen etching. (4) Epitaxial growth of single crystalline B12As2 was discovered and investigated on m-plane 15R-SiC inclusions in a 6H-SiC substrate wafer. SEM showed only one type of triangular feature on the smooth surface of the film which indicated single growth orientation of B12As2. This is confirmed by SWBXT and cross-sectional HRTEM which revealed untwinned (353) orientated B12As2, with significantly improved macroscopic properties as confirmed by Raman spectroscopy. The corresponding growth model involving the bonding configuration between the film and the substrate was developed. It was found that the choice of the unique film orientation substantially resulted from the tendency to nucleate in (111)B12As2 orientation on (474)15R-SiC close-packed facets that are exposed on the m-plane 15R-SiC surface. This indicates that m-plane 15R-SiC could be a potentially excellent substrate to grow high quality B12As2 for future device fabrication.