Charging and Discharging Channels in Photoluminescence Intermittency of Single Colloidal CdSe/CdS Core/Shell Quantum...

Understanding photoluminescence (PL) intermittency of single quantum dots (QDs) (intensity blinking by randomly switching between distinguishable brightness states under continuous excitation) has been a long-standing fundamental challenge and potential roadblock for their applications. Here we introduce a new analysis method for single-molecule spectroscopy that treats the blinking as photochemical/chemical processes (switching between neutral/bright and charged/dim states). It uncovers the channels for charging (bright to dim) and discharging (dim to bright) involved in PL blinking of single CdSe/CdS core/shell QDs. Both charging and discharging of the single CdSe/CdS core/shell QD possess a photochemical channel (∼10^-5 to 10^-6 events/photon) that linearly depends on excitation in both single- and multi-exciton regime. These two linear channels coupled to a spontaneous discharging channel (∼2 events/s) to dictate the QDs from nonblinking to gradually blinking under increasing excitation. For high-quality CdSe/CdS core/shell QDs, Auger ionization of multiexciton for both charging and discharging is negligible.