Exploiting Functional Impurities for Fast and Efficient Incorporation of Manganese into Quantum Dots

The incorporation of manganese (Mn) ions into Cd(Zn)-chalcogenide QDs activates strong spin-exchange interactions between the magnetic ions and intrinsic QD excitons that have been exploited for color conversion, sunlight harvesting, electron photoemission, and advanced imaging and sensing. The ability to take full advantage of novel functionalities enabled by Mn dopants requires accurate control of doping levels over a wide range of Mn contents. This, however, still represents a considerable challenge. Specific problems include the difficulty in obtaining high Mn contents, considerable broadening of QD size dispersion during the doping procedure, and large batch-to-batch variations in the amount of incorporated Mn. Here, we show that these problems originate from the presence of unreacted cadmium (Cd) complexes whose abundance is linked to uncontrolled impurities participating in the QD synthesis. After identifying these impurities as secondary phosphines, we modify the synthesis by introducing controlled amounts of "functional" secondary phosphine species. This allows us to realize a regime of nearly ideal QD doping when incorporation of magnetic ions occurs solely via addition of Mn-Se units without uncontrolled deposition of Cd-Se species. Using this method, we achieve very high per-dot Mn contents (>30% of all cations) and thereby realize exceptionally strong exciton-Mn exchange coupling with g-factors of ∼600.