Formation and stabilization of single-crystalline metastable AuGe phases in Ge nanowires

We use in situ observations by variable temperature transmission electron microscopy on AuGe alloy drops at the tips of Ge nanowires (NWs) with systematically varying composition to demonstrate the controlled formation of metastable solid phases integrated in NWs. The process, which operates in the regime of vapor-liquid-solid growth, involves a size-dependent depression of the alloy liquidus at the nanoscale that leads to extremely Ge-rich AuGe melts at low temperatures. During slow cooling, these liquid AuGe alloy drops show pronounced departures from equilibrium, i.e., a frustrated phase separation of Ge into the adjacent solid NW, and ultimately crystallize as single-crystalline segments of metastable γ-AuGe. Our findings demonstrate a general avenue for synthesizing NW heterostructures containing stable and metastable solid phases, applicable to a wide range of materials of which NWs form by the vapor-liquid-solid method.