Self-narrowing of size distributions of nanostructures by nucleation antibunching

We study theoretically the size distributions of ensembles of nanostructures fed from a nanosize mother phase or a nanocatalyst that contains a limited number of the growth species that form each nanostructure. In such systems, the nucleation probability decreases exponentially after each nucleation event, leading to the so-called nucleation antibunching. Specifically, this effect has been observed in individual nanowires grown in the vapor-liquid-solid mode and greatly affects their properties. By performing numerical simulations over large ensembles of nanostructures as well as developing two different analytical schemes (a discrete and a continuum approach), we show that nucleation antibunching completely suppresses fluctuation-induced broadening of the size distribution. As a result, the variance of the distribution saturates to a time-independent value instead of growing infinitely with time. The size distribution widths and shapes primarily depend on the two parameters describing the degree of antibunching and the nucleation delay required to initiate the growth. The resulting sub-Poissonian distributions are highly desirable for improving size homogeneity of nanowires. On a more general level, this unique self-narrowing effect is expected whenever the growth rate is regulated by a nanophase which is able to nucleate an island much faster than it is refilled from a surrounding macroscopic phase.