We report the Au catalyst-assisted synthesis of 20 μm long GaAs nanowires by the vapor-liquid-solid hydride vapor phase epitaxy (HVPE) exhibiting a polytypism-free zincblende phase for record radii lower than 15 nm down to 5 nm. HVPE makes use of GaCl gaseous growth precursors at high mass input of which fast dechlorination at the usual process temperature of 715 °C results in high planar growth rate (standard 30-40 μm/h). When it comes to the vapor-liquid-solid growth of nanowires, fast solidification at a rate higher than 100 μm/h is observed. Nanowire growth by HVPE only proceeds by introduction of precursors in the catalyst droplets from the vapor phase. This promotes almost pure axial growth leading to nanowires with a constant cylinder shape over unusual length. The question of the cubic zincblende structure observed in HVPE-grown GaAs nanowires regardless of their radius is at the heart of the paper. We demonstrate that the vapor-liquid-solid growth in our conditions takes place at high liquid chemical potential that originates from very high influxes of both As and Ga. This yields a Ga concentration systematically higher than 0.62 in the Au-Ga-As droplets. The high Ga concentration decreases the surface energy of the droplets, which disables nucleation at the triple phase line thus preventing the formation of wurtzite structure whatever the nanowire radius is.

GaN nanowires with exceptional lengths are synthesized by vapor-liquid-solid coupled with near-equilibrium hydride vapor phase epitaxy technique on c-plane sapphire substrates. Because of the high decomposition frequency of GaCl precursors and a direct supply of Ga through the catalyst particle, the growth of GaN nanowires with constant diameters takes place at an exceptional growth rate of 130 μm/h. The chemical composition of the catalyst droplet is analyzed by energy dispersive X-ray spectroscopy. High-resolution transmission electron microscopy and selective area diffraction show that the GaN nanowires crystallize in the hexagonal wurzite structure and are defect-free. GaN nanowires exhibit bare top facets without any droplet. Microphotoluminescence displays a narrow and intense emission line (1 meV line width) associated to the neutral-donor bound exciton revealing excellent optical properties of GaN nanowires.