Ligand-Induced Symmetry Breaking as the Origin of Multiexponential Photoluminescence Decay in CdSe Quantum Dots.

ABSTRACT

The bright photoluminescence (PL) of colloidal CdSe quantum dots (QDs) makes them interesting for optical applications. For most of them, well-defined PL properties, dominated by a single excitonic state, are required. However, in many PL experiments with QD ensembles, multiexponential decay was observed. On the basis of spin-orbit density functional theory and screened configuration interaction calculations, we show that highly symmetric and defect-free CdSe QDs with diameters of 1.7 and 2.0 nm possess a multiexponential low-temperature PL at the single-dot level. This is a consequence of ligand-induced symmetry breaking with a subsequent rearrangement of the lowest eight excitonic states in two sets of four singly degenerate excitonic states. For each set, the lowest state is dark and the other three are bright. We find that the splitting between the sets can be modified by the coverage and choice of the ligand, which facilitates the engineering of the PL properties of CdSe QDs.