Density Functional Theory Study of the Gas Phase and Surface Reaction Kinetics for the MOVPE Growth of GaAsBi.

The kinetics of chemical reactions occurring during the metal-organic vapor phase epitaxy (MOVPE) of GaAsBi have been studied using density functional theory (DFT). GaAsBi is a metastable semiconductor alloy that has potential applications in high-performance long-wavelength emitters. Its growth is complicated by the low solubility of Bi within the GaAs lattice, which leads to phase segregation under conventional III-V semiconductor growth conditions. In this study, the thermochemical and kinetic parameters of the gas-phase pyrolysis and surface reactions occurring in the MOVPE growth of GaAsBi from trimethyl bismuth, tertiary butyl arsine, and triethyl gallium are calculated from first-principles electronic structure and vibrational mode calculations. These calculations indicate that the pyrolysis products AsH and Bi(CH) are the principle sources for the deposition of their respective metallic elements. The surface-adsorbed methyl species and their interaction with the gas-phase pyrolysis products lead to the self-limiting growth described within this model. The calculated thermochemical and kinetic values provide initial parameters for the development of a microkinetic model of GaAsBi deposition.