Cluster-Seeded Synthesis of Doped CdSe:Cu4 Quantum Dots

We report here a method for synthesizing CdSe quantum dots (QDs) containing copper such that each QD is doped with four copper ions. The synthesis is a derivative of the cluster-seed method, whereby organometallic clusters act as nucleation centers for quantum dots. The method is tolerant of the chemical identity of the seed; as such, we have doped four copper ions into CdSe QDs using [Na(H2O)3]2[Cu4(SPh)6] as a cluster seed. The controlled doping allows us to monitor the photophysical properties of guest ions with X-ray spectroscopy, specifically XANES and EXAFS at the copper K-edge. These data reveal that copper can capture both electrons and holes from photoexcited CdSe QDs. When the dopant is oxidized, photoluminescence is quenched and the copper ions translocate within the CdSe matrix, which slows the return to an emissive state.