Phonon-Mediated and Weakly Size-Dependent Electron and Hole Cooling in CsPbBr(3) Nanocrystals Revealed by Atomistic Simulations and Ultrafast Spectroscopy

[Image: see text] We combine state-of-the-art ultrafast photoluminescence and absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate charge-carrier cooling in CsPbBr(3) nanocrystals over a very broad size regime, from 0.8 to 12 nm. Contrary to the prevailing notion that polaron formation slows down charge-carrier cooling in lead-halide perovskites, no suppression of carrier cooling is observed in CsPbBr(3) nanocrystals except for a slow cooling (over ∼10 ps) of “warm” electrons in the vicinity (within ∼0.1 eV) of the conduction band edge. At higher excess energies, electrons and holes cool with similar rates, on the order of 1 eV ps(–1) carrier(–1), increasing weakly with size. Our ab initio simulations suggest that cooling proceeds via fast phonon-mediated intraband transitions driven by strong and size-dependent electron–phonon coupling. The presented experimental and computational methods yield the spectrum of involved phonons and may guide the development of devices utilizing hot charge carriers.