Halogen Vacancies Enable Ligand‐Assisted Self‐Assembly of Perovskite Quantum Dots into Nanowires

Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide‐vacancy‐driven, ligand‐directed self‐assembly process of CsPbBr₃ PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface‐Br‐vacancy‐rich CsPbBr₃ PQDs self‐assemble into nanowires (NWs) that are 20–60 nm in width and several millimeters in length. The NWs exhibit a sharp photoluminescence profile (≈18 nm full‐width at‐half‐maximum) that peaks at 525 nm. Our findings provide insight into the defect‐correlated dynamics of PQDs and defect‐assisted fabrication of perovskite materials and devices.