Ligand-Controlled Phonon Dynamics in CsPbBr3 Nanocrystals Revealed by Machine-Learned Interatomic Potentials

Abstract

Halide perovskite nanocrystals are leading candidates for next-generation optoelectronics, yet the role of surface ligands in controlling their phonon dynamics remains poorly understood. These dynamics critically govern nonradiative relaxation, energy up-conversion, and phonon-assisted anti-Stokes emission. Conventional ab initio methods, while accurate, are computationally infeasible for experimentally relevant nanocrystal sizes that require thousands of atoms to capture realistic ligand shells and dynamic disorder at finite temperatures. Here, we introduce a machine- learned interatomic potential fine-tuned on small CsPbBr3 nanocrystals with diverse ligands, enabling accurate prediction of ligand-induced phonon properties far beyond the spatial and temporal scales of ab initio methods. We find that both cationic and anionic ligands systematically redshift Pb-Br-Pb stretching modes while blueshifting the PbBr64- octahedral rotation mode, with stronger overall effects for anionic passivation. Notably, anionic ligands stiffen the rotation mode non-monotonically with respect to the ligand binding energy. Our findings reveal important roles of cationic and anionic ligands in modulating key dynamic modes of halide perovskite nanocrystals associated with detrimental nonradiative losses, offering mechanistic insights and design principles for high-performance perovskite nanocrystal optoelectronics.