First-Principles Calculations of Luminescence Spectra of Real-Scale Quantum Dots

The luminescence line shape is an important feature of semiconductor quantum dots (QDs) and affects performance in various optical applications. Here, we report a first-principles method to predict the luminescence spectrum of thousands of atom QDs. In our approach, neural network potential calculations are combined with density functional theory calculations to describe exciton-phonon coupling (EPC). Using the calculated EPC, the luminescence spectrum is evaluated within the Franck-Condon approximation. Our approach results in the luminescence line shape for an InP/ZnSe core/shell QD (3406 atoms) that exhibits excellent agreement with the experiments. From a detailed analysis of EPC, we reveal that the coupling of both acoustic and optical phonons to an exciton are important in determining the spectral line shapes of core/shell QDs, which is in contrast with previous studies. On the basis of the present simulation results, we provide guidelines for designing high-performance core/shell QDs with ultrasharp emission spectra.