Size-dependent phase diagram of nanoscale alloy drops used in vapor--liquid--solid growth of semiconductor nanowires.

We use in situ observations during high-temperature transmission electron microscopy to quantify the exchange of semiconductor material between Au-Ge vapor--liquid--solid seed drops and Ge nanowires (NWs). By performing simultaneous measurements under identical conditions on arrays with systematic variations in NW diameter, we establish the nanoscale size dependence of the temperature-dependent equilibrium composition of the Au-Ge binary alloy. We find a significantly enhanced Ge solubility for drops on thin NWs compared to thicker ones. The controlled modification of the surface of the NW by an ordered carbon shell leads to drastic changes in the solubility.