On the Mechanism of Alkylammonium Ligands Binding to the Surface of CsPbBr(3) Nanocrystals

[Image: see text] CsPbBr(3) nanocrystals (NCs) suffer from instabilities caused by the dynamic and labile nature of both the inorganic core and the organic–inorganic interface. Surface ligand engineering thus remains an imminent research topic. In this study, classical molecular dynamics simulations with an explicit solvent are used to gain insights into the inherent binding properties of three different alkylammonium ligands—primary dodecylammonium (DA), secondary didodecylammonium (DDA), and quaternary dimethyldi- dodecylammonium (DMDDA). Our simulations uncover three main factors that govern the effective ligand–substrate interactions: (i) the ability of the head-group to penetrate into the binding pocket, (ii) the strength of head-group interactions with the polar solvent, and (iii) the higher barrier for ligand adsorption/desorption in the case of multiple alkyl chains. The interplay between these factors causes the following order of the binding free energies: DDA < DA ≈ DMDDA, while surface capping with DDA and DMDDA ligands is additionally stabilized by the kinetic barrier. These findings are in agreement with previous experimental observations and with the results of presented ligand-exchange experiments, wherein DDA is found to loosely bind to the CsPbBr(3) surface, while DMDDA capping is more stable than capping with the primary oleylammonium ligand. The presented mechanistic understanding of the ligand–NC interactions will aid in the design of cationic ligands that make perovskite NC surfaces more robust.