Sub-Bandgap Optical Modulation of Quantum Dot Blinking Statistics.

Abstract

Colloidal quantum dots (QDs) suffer from pervasive photoluminescence intermittency that frustrates applications and correlates with irreversible photodegradation. In single-QD spectroscopies, blinking manifests as sporadic switching between ON and OFF states without a characteristic time scale, and the longstanding search for mechanisms has been recently accelerated by techniques to controllably modulate the QD environment. Here, we develop an all-optical modulation scheme and demonstrate that sub-bandgap light tuned to the stimulated emission transition perturbs the blinking statistics of individual CdSe/ZnS core/shell QDs. Resonant optical modulation progressively suppresses long-duration ON events, quantified by a power-law slope that is more negative on average (ΔαON = 0.46 ± 0.09), while OFF distributions and truncation times are unaffected. This characteristic effect is robust to choices in background subtraction and statistical analysis but supports mechanistic descriptions beyond first-order kinetics. This demonstration of all-optical perturbation of QD blinking dynamics provides an experimental avenue to disentangle the complex photophysics of photoluminescence intermittency.