Epitaxial Si nanowires grown from Au seeds using the vapor-liquid-solid method begin growing normal to the Si(111) substrate atop a tapered base. After a kinetically determined length, the NWs may kink away from [111] to another crystallographic direction. The smallest NWs prefer growth along 110 while larger Si NWs choose either 111 or 112 based on whether growth conditions favor Au-free sidewalls. "Vertical" growth normal to the Si(111) substrate is obtained only for slowly growing NWs with Au-decorated sidewalls. At the fastest growth rates, single-crystal Si NWs smoothly, continuously, and randomly vary their growth directions, producing a morphology that is qualitatively different than highly kinked growth.

Vapor-liquid-solid growth of high-quality Si nanowires relies on the stability of the liquid metal seed. In situ transmission electron microscopy shows that liquid AuSi seed spreads along the sidewalls of Si nanowires for some growth conditions. This liquid thin film phase separates to form solid Au clusters as the nanowire is quenched below the solidus temperature. The length that the liquid film spreads from the seed and its thickness can be explained by considering the spreading thermodynamics of droplets on cylinders.

We identify a previously uncharacterized vapor-liquid-solid growth mode that can produce small diameter, epitaxial ⟨110⟩ oriented Si and Ge nanowires (NWs). Disilane or digermane pyrolysis evolves H2 causing the monolayer thick Au/Si(111) layer between three dimensional Au seeds to dewet and form small Au islands. Under some conditions, these small islands facilitate “seedless” growth of small diameter NWs distinct from larger NWs that grow from the deposited seeds leading to a bimodal diameter distribution. We identify the precursor pressures and growth temperature regimes for which Si and Ge NW growth occurs in the absence of deposited seeds from the dewetted Au/Si(111) layer.

The presence and configuration of Au on the sidewalls of vapor-liquid-solid grown Si nanowires (NWs) was investigated using analytical (scanning) transmission and scanning electron microscopy. The relationship between growth conditions and Au/Si interface thermodynamics is shown to have a profound effect on NW growth. For some growth conditions, liquid AuSi can spread from the seed at the NW tip along the sidewalls during growth. This liquid film will phase separate and solidify, forming small Au clusters as the NW is cooled from the growth temperature. Growth conditions are correlated with the variety of Au cluster configurations found. The observed behavior can be explained by considering the thermodynamics of droplet spreading on cylinders.

Hole accumulation in Ge/Si core/shell nanowires (NWs) has been observed and quantified using off-axis electron holography and other electron microscopy techniques. The epitaxial [110]-oriented Ge/Si core/shell NWs were grown on Si (111) substrates by chemical vapor deposition through the vapor-liquid-solid growth mechanism. High-angle annular-dark-field scanning transmission electron microscopy images and off-axis electron holograms were obtained from specific NWs. The excess phase shifts measured by electron holography across the NWs indicated the presence of holes inside the Ge cores. Calculations based on a simplified coaxial cylindrical model gave hole densities of (0.4 ± 0.2) /nm(3) in the core regions.