Manipulation of hot-carrier cooling dynamics in CsPbBr3 quantum dots via site-selective ligand engineering

Abstract

Prolonging the lifetime of photoinduced hot carriers in lead–halide perovskite quantum dots (QDs) is highly desirable because it can help improve the photovoltaic conversion efficiency. Ligand engineering has recently become a promising strategy to achieve this; nevertheless, mechanistic studies in this field remain limited. Herein, we propose a new scenario of ligand engineering featuring Pb2+/Br− site-selective capping on the surface of CsPbBr3 QDs. Through joint observations of temperature-dependent photoluminescence, ultrafast transient absorption, and Raman spectroscopy of the two contrasting model systems of CsPbBr3 QDs (i.e., capping with organic ligand only vs hybrid organic/inorganic ligands), we reveal that the phononic regulation of Pb–Br stretching at the Br-site (relative to Pb-site) leads to a larger suppression of charge–phonon coupling due to a stronger polaronic screening effect, thereby more effectively retarding the hot-carrier cooling process. This work opens a new route for the manipulation of hot-carrier cooling dynamics in perovskite systems via site-selective ligand engineering.