Directed synthesis of germanium oxide nanowires by vapor-liquid-solid oxidation

We report on the directed synthesis of germanium oxide (GeO(x)) nanowires (NWs) by locally catalyzed thermal oxidation of aligned arrays of gold catalyst-tipped germanium NWs. During oxygen anneals conducted above the Au-Ge binary eutectic temperature (T > 361 °C), one-dimensional oxidation of as-grown Ge NWs occurs by diffusion of Ge through the Au-Ge catalyst droplet, in the presence of an oxygen containing ambient. Elongated GeO(x) wires grow from the liquid catalyst tip, consuming the adjoining Ge NWs as they grow. The oxide NWs' diameter is dictated by the catalyst diameter and their alignment generally parallels that of the growth direction of the initial Ge NWs. Growth rate comparisons reveal a substantial oxidation rate enhancement in the presence of the Au catalyst. Statistical analysis of GeO(x) nanowire growth by ex situ transmission electron microscopy and scanning electron microscopy suggests a transition from an initial, diameter-dependent kinetic regime, to diameter-independent wire growth. This behavior suggests the existence of an incubation time for GeO(x) NW nucleation at the start of vapor-liquid-solid oxidation.