The metalorganic chemical vapor deposition (MOCVD) of epitaxial III‐V semiconductor alloys on III‐V substrates is reviewed in detail. The emphasis is placed on both practical and theoretical knowledge of the equipment and deposition process. The chemistry of the source alkyls and the dynamics of the transport process are discussed. The growth of the GaAs and AlxGa1−xAs systems are treated as prototypical examples (and the most studied) of the III‐V materials. Latter sections review InP, Ga1−xInxAs, and related alloys. Finally, the antimonide and the other systems are reviewed. Electronic and optical devices fabricated from MOCVD‐grown materials are used as examples of the capabilities of the growth technique.

Metalorganic chemical vapor deposition of III‐V semiconductors

High purity GaAs prepared from trimethylgallium and arsine

A study of the growth mechanism of epitaxial GaAs as grown by the technique of metal organic vapour phase epitaxy

A major limitation to the continuing development of organometallic vapor phase epitaxy (OMVPE) for the growth of III/V semiconductor materials is the hazard posed by the hydride sources, AsH3 and PH3, which are virtually universally used, in high pressure cylinders, as the group V source materials for the growth of the highest quality materials. The ideal group V source would be a nontoxic liquid with a moderate vapor pressure (50-500 Torr). To be suitable for OMVPE growth, the molecule must pyrolyze at ordinary growth temperatures, be stable against decomposition in the bottle at room temperature, and not participate in undesirable parasitic reactions with the group III source molecules. The new sources have additional constraints related to purity. They must be easily purified without decomposing and produce no detectable carbon contamination in the resultant epitaxial layers. This set of stringent requirements eliminates most commonly available non-hydride group V sources. Recent research on newly developed sources has shown considerable promise. The entire area of group V sources, including the elemental sources, for OMVPE growth of III/V materials will be reviewed. The sources with no hydrogen atoms attached to the group V atom, the elemental, trimethyl-V, and triethyl-V, sources all appear to give unacceptably high carbon incorporation. Diethylarsine, which has one H attached to the As, produces high quality GaAs but has an inconveniently low vapor pressure. Trimethylphosphine and triethylphosphine o not pyrolyze at low enough temperatures to be useful for conventional OMVPE growth. Tertbutylarsine (TBAs) and tertbutylphosphine (TBP) appear to be promising source materials. TBP has a very low toxicity, a vapor pressure ideal for OMVPE growth, and the pyrolysis occurs at lower temperatures than for PH3, allowing the use of low values of V/III ratio for the growth of high quality material. No carbon contamination can be attributed to the TBP. Control of the As/P ratio in OMVPE grown GaAsP is much improved for TBP as compared with PH3 due to the more rapid pyrolysis. At normal growth temperatures the P distribution coefficient is nearly unity. TBAs has been less studied, but appears to have similar attributes including a favorable vapor pressure and lower pyrolysis temperature than AsH3, allowing OMVPE growth of GaAs at low values of V/III ratio. The substitution of TBAs for AsH3 results in no observable increase in carbon in the epitaxial GaAs.

H.T. Hall

Papers

OMVPE growth of AlxGa1−xAs