Electrochemically controlled auger quenching of Mn²+ photoluminescence in doped semiconductor nanocrystals

Auger processes in colloidal semiconductor nanocrystals have been scrutinized extensively in recent years. Whether involving electron-exciton, hole-exciton, or exciton-exciton interactions, such Auger processes are generally fast and hence have been considered prominent candidates for interpreting fast processes relevant to photoluminescence blinking and multiexciton decay. With recent advances in the chemistries of nanocrystal doping, increasing attention is now being paid to analogous photophysical properties of colloidal-doped semiconductor nanocrystals. Here, we report the first investigation of the effects of electron-dopant exchange interactions on dopant luminescence in doped semiconductor nanocrystals. Using electrochemical techniques, electrical control of charge-carrier densities in films of colloidal Mn(2+)-doped CdS quantum dots has been achieved and used to demonstrate remarkably effective Auger de-excitation of photoexcited Mn(2+). The doped nanocrystals are found to be substantially more sensitive to Auger de-excitation than their undoped analogues, a result shown to arise primarily from the long Mn(2+) excited-state lifetime. This observation of exceptionally effective Auger quenching has broader implications in areas of high-power, single-particle, or electrically driven luminescence of doped semiconductor nanocrystals, and also suggests interesting opportunities for modulating Mn(2+) photoluminescence intensities on sublifetime time scales, or for imaging charge carriers in nanocrystal-based devices.