Improving the Stability of Colloidal CsPbBr3 Nanocrystals with an Alkylphosphonium Bromide as Surface Ligand Pair

In this study, we synthesized a phosphonium-based ligand, trimethyl(tetradecyl)phosphonium bromide (TTP-Br), and employed it in the postsynthesis surface treatment of Cs-oleate-capped CsPbBr₃ nanocrystals (NCs). The photoluminescence quantum yield (PLQY) of the NCs increased from ∼60% to more than 90% as a consequence of replacing Cs-oleate with TTP-Br ligand pairs. Density functional theory calculations revealed that TTP⁺ ions bind to the NC surface by occupying Cs⁺ surface sites and orienting one of their P–CH₃ bonds perpendicular to the surface, akin to quaternary ammonium passivation. Importantly, TTP-Br-capped NCs exhibited higher stability in air compared to didodecyldimethylammonium bromide-capped CsPbBr₃ NCs (which are considered a benchmark system), retaining ∼90% of their PLQY after 6 weeks of air exposure. Light-emitting diodes fabricated with TTP-Br-capped NCs achieved a maximum external quantum efficiency of 17.2%, demonstrating the potential of phosphonium-based molecules as surface ligands for CsPbBr₃ NCs in optoelectronic applications.