Thermodynamics Controlled Sharp Transformation from InP to GaP Nanowires via Introducing Trace Amount of Gallium

Growth of high-quality III-V nanowires at a low cost for optoelectronic and electronic applications is a long-term pursuit of research. Still, controlled synthesis of III-V nanowires using chemical vapor deposition method is challenge and lack theory guidance. Here, we show the growth of InP and GaP nanowires in a large area with a high density using a vacuum chemical vapor deposition method. It is revealed that high growth temperature is required to avoid oxide formation and increase the crystal purity of InP nanowires. Introduction of a small amount of Ga into the reactor leads to the formation of GaP nanowires instead of ternary InGaP nanowires. Thermodynamic calculation within the calculation of phase diagrams (CALPHAD) approach is applied to explain this novel growth phenomenon. Composition and driving force calculations of the solidification process demonstrate that only 1 at.% of Ga in the catalyst is enough to tune the nanowire formation from InP to GaP, since GaP nucleation shows a much larger driving force. The combined thermodynamic studies together with III-V nanowire growth studies provide an excellent example to guide the nanowire growth.