Interplay of Kinetic and Thermodynamic Factors in the Stationary Composition of Vapor-Liquid-Solid IIIVxV1-x Nanowires.

Compositional control over vapor-liquid-solid III-V ternary nanowires based on group V intermix (VLS IIIV_xV_1-x NWs) is complicated by the presence of a catalyst droplet with extremely low and hence undetectable concentrations of group V atoms. The liquid-solid and vapor-solid distributions of IIIV_xV_1-x NWs at a given temperature are influenced by the kinetic parameters (supersaturation and diffusion coefficients in liquid, V/III flux ratio in vapor), temperature and thermodynamic constants. We analyze the interplay of the kinetic and thermodynamic factors influencing the compositions of VLS IIIV_xV_1-x NWs and derive a new vapor-solid distribution that contains only one parameter of liquid, the ratio of the diffusion coefficients of dissimilar group V atoms. The unknown concentrations of group V atoms in liquid have no influence on the NW composition at high enough levels of supersaturation in liquid. The simple analytic shape of this vapor-solid distribution is regulated by the total V/III flux ratio in vapor. Calculating the temperature-dependent desorption rates, we show that the purely kinetic regime of the liquid-solid growth occurs for VLS IIIV_xV_1-x NWs in a wide range of conditions. The model fits the data well on the vapor-solid distributions of VLS InP_xAs_1-x and GaP_xAs_1-x NWs and can be used for understanding and controlling the compositions of any VLS IIIV_xV_1-x NWs, as well as modeling the compositional profiles across NW heterostructures in different material systems.