  We develop a nucleation-based model to explain the formation of the wurtzite
(WZ) crystalline phase during the vapor-liquid-solid growth of free-standing
nanowires of zinc-blende (ZB) semiconductors. We first show that, in nanowires,
nucleation generally occurs at the outer edge of the solid/liquid interface
(the triple phase line) rather than elsewhere at the solid/liquid interface. In
the present case, this entails major differences between ZB and WZ nuclei.
Depending on the pertinent interface energies, WZ nucleation is favored at high
liquid supersaturation. This explains our systematic observation of ZB during
the early stages of nanowire growth.
