<p>Free-standing single crystals of bulk GaN were grown via unseeded vapor phase transport at 1130C on hexagonal BN surfaces via direct reaction of Ga with ammonia. The temperature and stability of the Ga source were critical in terms of uniform nucleation and growth. The source temperature was maintained at 1260C to minimize a rapid reaction leading to the formation of GaN and the subsequent decomposition beneath the surface and consequent spattering of Ga. A maximum crystal growth temperature of 1130C was determined in which the GaN growth kinetics were much greater than decomposition. The number of nucleation events was reduced and the crystal size increased by a novel nucleation technique wherein ammonia was introduced at high temperatures. The resulting crystals were either needles or platelets depending on the process variables employed. Low V/III ratios achieved via ammonia flow rates 75sccm and/or ammonia total pressures 430Torr favored lateral growth. The average lateral growth rate for the platelets was ~50micron/hr; the average vertical growth rate for the needles was ~500micron/hr. Growth rates in all other directions for each of these two morphologies were very low. Seeded growth of both needle and platelet crystals was also achieved; however, the growth rate decreased at longer times and higher pressures due to reaction with hydrogen from the increased decomposition of ammonia. Nitrogen dilution of ammonia reduced the amount of hydrogen generated as a result of ammonia decomposition and increased the kinetic barrier to desorption of reactants from the GaN surface and then alleviated the enhanced decomposition of GaN crystals. A 2mm x 1.5mm needle and a 2.3mm x 1.8mm x 0.3mm platelet of GaN were grown with minimal decomposition in a 66.7% ammonia + 33.3% nitrogen gas mixture. Excellent crystalline quality was confirmed by Raman spectroscopy and Photoluminescence.Crystal growth using a Ga- 5at%Al source was conducted in an attempt to increase growth rate and inhibit decomposition. No notable change in growth rate was observed and hollow crystals were formed, indicating that Al promotes vertical growth under otherwise similar conditions for GaN growth. In addition, fine-grained AlN was formed within the binary Ga-Al source, thus, the supply of Al was progressively reduced. Nucleation control via addition of Si resulted in a slightly reduced number of larger crystals. X-ray Photoelectron Spectroscopy suggested that amorphous silicon nitride was formed on the BN substrate and nucleation rate was slightly reduced. Silicon was not detected within the sensitivity of Energy Dispersive Spectroscopy. Raman spectroscopy revealed insignificant amount of Si present in the crystal. Smoother surface morphology of the crystals grown in the presence of Si was observed by Scanning Electron Microscopy.<P>
| Identifer | oai:union.ndltd.org:NCSU/oai:NCSU:etd-20010706-210436 |
| Date | 10 July 2001 |
| Creators | Shin, Hyunmin |
| Contributors | Robert F. Davis, Zlatko Sitar, Jagannadham Kasichainula, Salah M. Bedair |
| Publisher | NCSU |
| Source Sets | North Carolina State University |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://www.lib.ncsu.edu/theses/available/etd-20010706-210436 |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to NC State University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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