Interplay of Quantum Confinement and Strain Effects in Type I to Type II Transition in GeSi Core–Shell Nanocrystals

[Image: see text] The electronic properties of hydrogenated, spherical SiGe and GeSi core–shell nanocrystals, with a diameter ranging from 1.8 to 4.0 nm, are studied within density functional theory. Effects induced by quantum confinement and strain on the near-band-edge state localization, as well as the band-offset properties between Si and Ge regions, are investigated in detail. On the one hand, we prove that SiGe core–shell nanocrystals always show a type II band-offset alignment, with the HOMO mainly localized on the Ge shell region and the LUMO mainly localized on the Si core region. On the other hand, our results point out that a type II offset cannot be observed in small (diameter less than 3 nm) GeSi core–shell nanocrystals. In these systems, quantum confinement and strain drive the near-band-edge states to be mainly localized on Ge atoms, i.e., in the core region. In larger GeSi core–shell nanocrystals, instead, the formation of a type II offset can be engineered by playing with both core and shell thickness. The factors which determine the band-offset character at the Ge/Si interface are discussed in detail.