Spontaneous atomic ordering in MOVPE grown GaAsSb

Spontaneous atomic ordering of semiconductor alloys is of great practical and fundamental interest. Atomic ordering of III-V alloys such as InGaP has been extensively studied experimentally and theoretically. In this thesis, we investigate a little-studied, atomic-ordering phenomenon, the so-called CuAu structure in the III-V material GaAsSb, grown by the technique of metalorganic vapor-phase epitaxy(MOVPE). Despite being first observed in 1986 in this material, there is as yet no detailed microscopic model for its formation mechanism. A key part of the thesis involves the study of surfactant effects on the ordering process in GaAsSb. Surfactants are elements which modify the growth surface without incorporation in the bulk. Nevertheless, they influence the incorporation of the bulk elements. We first explored the surfactant behavior of Bi on GaAs in order to understand how Bi incorporates at the surface and in the bulk in a related III-V material. For GaAs(001), Bi surface layers are stable at temperatures below 500C but rapidly desorb at temperatures of 550C and higher. Bi coverages of over 1ML induce the formation of Bi islands, whose sizes increase with increasing Bi exposure. Bulk incorporation of Bi remains essentially zero at typical MOVPE growth temperatures. In the case of GaAsSb alloys, Bi surfactant was found to induce CuAu ordering, with no measurable Bi incorporation in the bulk. High resolution TEM was used to study the detailed microstructural features for ordered and disordered samples. The domain sizes of the ordered regions are from 5nm to 20nm under all growth conditions. In contrast to orderings in other alloys such as InGaP, CuAu ordering had no observable effect on the bandgap. CuAu ordering in GaAsSb was studied in a function of growth conditions, including Bi surfactant concentration, growth temperature, growth rate, and substrate miscut. All of these experiments confirm that bulk CuAu ordering is a surface driven, rather than bulk process. It is unlikely that the ordering mechanism is similar to the dimer-induced strain models that have been successfully used to explain CuPt ordering in InGaP. We propose a simple model based on alternating incorporation of group V adatoms at step edges.