Achieving quantum confinement by bottom-up growth of nanowires has so far been limited to the ability of obtaining stable metal droplets of radii around 10 nm or less. This is within reach for gold-assisted growth. Because of the necessity to maintain the group III droplets during growth, direct synthesis of quantum sized structures becomes much more challenging for self-assisted III-V nanowires. In this work, we elucidate and solve the challenges that involve the synthesis of gallium-assisted quantum-sized GaAs nanowires. We demonstrate the existence of two stable contact angles for the gallium droplet on top of GaAs nanowires. Contact angle around 130° fosters a continuous increase in the nanowire radius, while 90° allows for the stable growth of ultrathin tops. The experimental results are fully consistent with our model that explains the observed morphological evolution under the two different scenarios. We provide a generalized theory of self-assisted III-V nanowires that describes simultaneously the droplet shape relaxation and the NW radius evolution. Bistability of the contact angle described here should be the general phenomenon that pertains for any vapor-liquid-solid nanowires and significantly refines our picture of how nanowires grow. Overall, our results suggest a new path for obtaining ultrathin one-dimensional III-V nanostructures for studying lateral confinement of carriers.
Keywords: III−V semiconductors on silicon; crystal structure; droplet size engineering; growth modeling; nanoneedles; nanowires; regular arrays; self-assisted growth.