The possibility of precisely manipulating interior nanospace, which can be adjusted by ligand-attaching down to the subnanometer regime, in a hyperstructured quantum dot (QD) superlattice (QDSL) induces a new kind of collective resonant coupling among QDs and opens up new opportunities for developing advanced optoelectric and photovoltaic devices. Here, we report the first real-time dynamics simulations of the multiple exciton generation (MEG) in one-, two-, and three-dimensional (1D, 2D, and 3D) hyperstructured H-passivated Si QDSLs, accounting for thermally fluctuating band energies and phonon dynamics obtained by finite-temperature ab initio molecular dynamics simulations. We computationally demonstrated that the MEG was significantly accelerated, especially in the 3D QDSL compared to the 1D and 2D QDSLs. The MEG acceleration in the 3D QDSL was almost 1.9 times the isolated QD case. The dimension-dependent MEG acceleration was attributed not only to the static density of states but also to the dynamical electron-phonon couplings depending on the dimensionality of the hyperstructured QDSL, which is effectively controlled by the interior nanospace. Such dimension-dependent modifications originated from the short-range quantum resonance among component QDs and were intrinsic to the hyperstructured QDSL. We propose that photoexcited dynamics including the MEG process can be effectively controlled by only manipulating the interior nanospace of the hyperstructured QDSL without changing component QD size, shape, compositions, ligand, etc.
Keywords: electron−phonon coupling; multiple exciton generation; photovoltaic efficiency; quantum dot superlattice; quantum resonance; time-dependent density functional theory.