AbstractWe investigated the nucleation of Ga droplets on singular GaAs(111)A substrates in the view of their use as the seeds for the self-assembled droplet epitaxial quantum dots. A small critical cluster size of 1–2 atoms characterizes the droplet nucleation. Low values of the Hopkins-Skellam index (as low as 0.35) demonstrate a high degree of a spatial order of the droplet ensemble. Around $350\,^{∘ }\hbox {C}$ 350 ∘ C the droplet size distribution becomes bimodal. We attribute this observation to the interplay between the local environment and the limitation to the adatom surface diffusion introduced by the Ehrlich–Schwöbel barrier at the terrace edges.