AbstractFormation and properties of quantum dots (QDs) and related nanostructures by conventional molecular beam epitaxy (MBE) and two other variants of the technique, have been systematically investigated. While MBE growth of CdSe on ZnSe at 300 °C results in the formation of rough CdSe quantum‐well‐like structures, by one of the variants, which combines epitaxial growth of a CdSe layer at 230 °C and subsequent in‐situ annealing at 310‐340 °C, tiny but distinct three‐dimensional (3D) QDs are formed. We demonstrate that QD formation by this method, developed originally by Rabe et al. (J. Cryst. Growth 184/185, 248 (1998) [30]), essentially takes place during the annealing step, by a process of “controlled roughening” of the as‐grown quasi‐two‐dimensional (2D) CdSe layer. In comparison to conventional MBE, this process results in reduction of the areal density of the self‐organized QDs by up to two orders of magnitude, thus making them distinctly discernible. In the second variant technique, similar to that applied originally for the self‐organization of CdTe/ZnTe quantum dots by Tinjod et al. (Appl. Phys. Lett. 82, 4340 (2003) [34], QD‐formation takes place as a result of deposition of an amorphous group‐VI layer onto a strained 2D CdSe layer at ∼ 50 °C, and its subsequent re‐desorption at temperatures of 280‐320 °C. While deposition and desorption of amorphous Se leads to the formation of large isolated QDs, we show that use of amorphous Te results in the self‐assembly and ordering of a rich variety of nanostructures. Luminescence, morphology, and composition of QDs and the underlying formation mechanism of the three processes are discussed in detail. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)