Temperature dependence of hot-carrier relaxation in PbSe nanocrystals: An ab initio study

Temperature-dependent dynamics of phonon-assisted relaxation of hot carriers, both electrons and holes, is studied in a PbSe nanocrystal using ab initio time-domain density-functional theory. The electronic structure is first calculated, showing that the hole states are denser than the electron states. Fourier transforms of the time-resolved energy levels show that the hot carriers couple to both acoustic and optical phonons. At higher temperature, more phonon modes in the high-frequency range participate in the relaxation process due to their increased occupation number. The phonon-assisted hot-carrier relaxation time is predicted using nonadiabatic molecular dynamics, and the results clearly show a temperature-activation behavior. The complex temperature dependence is attributed to the combined effects of the phonon occupation number and the thermal expansion. Comparing the simulation results with experiments, we suggest that the multiphonon relaxation channel is efficient at high temperature, while the Auger-type process may dominate the relaxation at low temperature. This combined mechanism can explain the weak temperature dependence at low temperature and stronger temperature dependence at higher temperature.