Ultraefficient Singlet Oxygen Generation from Manganese-Doped Cesium Lead Chloride Perovskite Quantum Dots

Lead halide perovskites hold promise for photovoltaics, lasers, and light-emitting diode (LED) applications, being known as light-harvesting or -emitting materials. Here we show that colloidal lead halide CsPbCl3 perovskite quantum dots (PQDs), when incorporating divalent manganese (Mn2+) ions, are able to produce spin-paired singlet oxygen molecules with over-unit quantum yield (∼1.08) in air conditions. Our mechanistic studies and atomic-level density functional theory calculations endorse an energy-migration-mediated quantum cutting process favoring multiple singlet oxygen generation (MSOG), in which one exciton-activated bulk Mn2+ ion (∼2.0 eV) inside the nanocrystal migrates its energy among the Mn2+ sublattice to two surface Mn2+ defect states (∼1.0 eV), followed by nonradiative energy transfers to two surrounding oxygen molecules. Moreover, superhydrophobicization of MSOG PQDs through silica-mediated polystyrene encapsulation prevents them from disintegrating in aqueous medium, enabling photodegradation of methyl orange at a rate even higher than that of the canonical titanium oxide photocatalyst. The observation of ultraefficient singlet oxygen generation in PQDs has implications for fields ranging from photodynamic therapy to photocatalytic applications.