We report the controllable growth of GaAs quantum complexes in droplet molecular-beam epitaxy, and the optical properties of self-assembled AlxGaAs quantum rings embedded in a superlattice. We found that Ga droplets on a GaAs substrate can retain their geometry up to a maximum temperature of 490 °C during post-growth annealing, with an optimal temperature of 320 °C for creating uniform and symmetric droplets. Through controlling only the crystallisation temperature under As4 in the range of 450 °C to 580 °C, we can reliably control diffusion, adsorption and etching rates to produce various GaAs quantum complexes such as quantum dots, dot pairs and nanoholes. AlxGaAs quantum rings are also realised within these temperatures via the adjustment of As beam equivalent pressure. We found that crystallisation using As2 molecules in the place of As4 creates smaller diameter quantum rings at higher density. The photoluminescence of As2 grown AlxGaAs quantum rings embedded in a superlattice shows a dominant emission from the quantum rings at elevated temperatures. This observation reveals the properties of the quantum ring carrier confinement and their potential application as efficient photon emitters.