Control of hot carrier relaxation in CsPbBr${}_3$ nanocrystals using damping ligands

In photon-conversion processes, rapid cooling of photo-induced hot carriers is a dominant energy loss channel. We herein report a 3-fold reduced hot carrier cooling rate in CsPbBr${}_3$ nanocrystals capped with a cross-linked polysiloxane shell in comparison to single alkyl-chain oleylamine ligands. Relaxation of hot charge carriers depends on the carrier-phonon coupling (CPC) process as an important channel to dissipate energies in nanostructured perovskite materials. The CPC strengths in the two samples were measured through cryogenic photoluminescence spectroscopic measurements. The effect of organic ligands on the CPC in CsPbBr${}_3$ nanocrystals is elucidated based on a damped oscillation model. This supplements the conventional polaron-based CPC model, by involving a damping effect on the CPC from the resistance of the ligands against nanocrystal lattice vibrations. The model also accounts for the observed linear temperature-dependence of the CPC strength. Our work enables predictions about the effect of the ligands on the performance of perovskite nanocrystals in future applications. (© 2022 Wiley‐VCH GmbH)