Surface and confinement effects on the optical and structural properties of silicon nanocrystals

In this work we investigate, by first-principles calculations, the structural, electronic and optical properties of: (1) oxygenated silicon-based nanoclusters of different sizes in regime of multiple oxidation at the surface, and (2) hydrogenated Si nanoclusters (H-Si-nc) in their ground and excited state configurations. Structural relaxations have been fully taken into account in all cases through total energy pseudopotential calculations within density functional theory.In the first case we have varied systematically the number of Si=O bonds at the cluster surface and found a nonlinear reduction of the energy gap with the Si=O bond number. A saturation limit is reached, which allows us to provide a consistent interpretation of the photoluminescence (PL) redshift observed in oxidized porous silicon samples. Our results help also to explain some very recent findings on the single silicon quantum dot photoluminescence bandwidth