Simultaneous Cationic and Anionic Ligand Exchange For Colloidally Stable CsPbBr3 Nanocrystals

Postsynthesis ligand exchange has been employed extensively on lead halide perovskite (LHP) nanocrystals (NCs), but the complex ligand shell composition of the starting NCs prevented a clear understanding of the exchange process, and the surface chemistry of the final NCs remained poorly characterized. Here, we describe a ligand exchange strategy involving the displacement of both cationic and anionic ligands on native model systems of CsPbBr3 NCs, which are exclusively coated with Cs-oleate. These ligands are exchanged with various quaternary ammonium bromides (R4NBr), and complete exchange is confirmed by nuclear magnetic resonance (NMR) spectroscopy analysis. The displacement of the native Cs-oleate ligands with proton-free R4NBr delivers NCs with excellent colloidal stability and near-unity PLQY, which is preserved after washing with polar solvents, over 3 weeks of storage in air, and after heating a solution of NCs to 80 °C, as confirmed by NMR analysis. The results, together with density functional theory calculations, suggest that the higher stability of quaternary ammonium capped NCs is not due to a stronger binding interaction to the surface but rather to weaker solvent–ligand interactions of R4NBr compared to Cs-oleate, driving the former to the surface of the NCs.