MOCVD Growth and Characterization of Gallium Nitride and Gallium Antimonide Nanowires

Open Access
Author:
Burke, Robert
Graduate Program:
Materials Science and Engineering
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
October 06, 2008
Committee Members:
  • Joan Marie Redwing, Dissertation Advisor
  • Suzanne E Mohney, Committee Member
  • Elizabeth C Dickey, Committee Member
  • Joan Marie Redwing, Committee Chair
  • Jian Xu, Committee Member
Keywords:
  • GaSb
  • nanowires
  • MOCVD
  • GaN
Abstract:
Group-III nitride and group-III antimonide thin films have been used for years in optoelectronic, high-speed applications, and high power/high temperature applications such as light emitting diodes (LEDs), microwave power devices, and thermovoltaics. In recent years, nanowires have gained interest due to the ability to take advantage of their geometry for increased light absorption and the synthesis of radial heterostructures. Several growth techniques have been explored for the growth of GaN and GaSb nanowires. Metal-organic chemical vapor deposition (MOCVD) is of particular interest due to its use in the commercial growth and fabrication of GaN-based and GaSb-based devices. The first part of this thesis focused on addressing several key issues related to the growth of GaN nanowires by MOCVD. Preliminary studies investigated the effect of growth conditions on GaN nanowire formation in a hot wall MOCVD reactor. A computational fluid dynamics-based model was developed to predict the gas phase velocity, temperature and concentration profiles in the reactor. The results demonstrate a strong dependence of GaN nanowire growth on substrate position within the reactor which is due to the rapid reaction and depletion of precursors near the gas inlet of the reactor. Ni-catalyzed GaN nanowire growth was observed to occur over the temperature range of 800-900oC, which is significantly lower than typical GaN thin film temperatures. The nanowires, however, exhibited a tapered diameter due to thin film deposition which occurred simultaneously with nanowire growth. Based on the low growth temperatures, TEM characterization was carried out to investigate the nature of the catalyst. Through these studies, the catalyst was found to consist of Ni3Ga, indicating the presence of a vapor-solid-solid growth mechanism. In an attempt to improve the nanowire growth selectivity, GeCl4 was added during growth resulting in a drastic increase in nanowire density and a reduction in the tapering of the nanowires. Upon further inspection with TEM, the nanowires were found to consist of two morphologies: smooth nanowires and serrated nanowires. The smooth nanowires were found to consist of the wurtzite crystal structure, while the serrated nanowires were determined to have a wurtzite core with zinc blende faceted islands protruding from the wurtzite core. The second half of this thesis focused on the growth and characterization of GaSb nanowires. An extensive amount of work has been carried out on GaSb thin films, however only a few reports exist on GaSb nanowire growth. As a result, it was necessarily to complete a systematic study to determine a growth window for GaSb nanowires. A narrow range of growth conditions were found for Au-catalyzed GaSb nanowire growth. Vertically oriented nanowires were observed over a pressure range of 150-300 Torr depending on the substrate. Based on these findings, additional characterization was carried out to investigate the structural properties of the nanowires along with chemical analysis of the catalyst to determine the nature of the catalyst as a function of the growth conditions. The catalyst was found to consist of Ga, Sb, and Au consistent with that expected for vapor-liquid-solid growth, however the concentrations varied depending on the growth conditions and nanowire sample. For one set of nanowires, the seed particle contained a Au-Sb solid solution (1-15 at.% Sb). For the other set of nanowires, the particle consisted of an AuSb2 grain and an AuGa or Au2Ga grain that resulted in the formation of a bicrystalline nanowire. Photoluminescence measurements were also obtained on these samples and compared to the thin film literature. Samples grown on Si (111) were found to possess good optical properties, while samples grown on sapphire substrates were dominated by native defect transitions. The optical quality of the nanowire sample was also found to have a significant dependence on the V/III ratio.