Collective Blinking of Upconversion Emission in Lanthanide-doped Nanocrystals

Abstract

Fluorescence blinking, often regarded as a limitation for stable emitters, can enable super-resolution localization microscopy and serve as a versatile reporter of the photophysical states of quantum emitters and their interactions with local environment. However, conventional blinking emitters are typically single quantum systems with Stokes-shifted fluorescence, making them susceptible to autofluorescence background, weak signal, and irreversible photodegradation under prolonged excitation. In contrast, single lanthanide-doped upconversion nanocrystals are effectively background-free anti-Stokes emitters and demonstrate robust resistance to photodegradation, yet they are generally considered non-blinking owing to the presence of a large ensemble of uncorrelated emitting lanthanide ions within a single nanocrystal. Here we report the discovery and control of collective blinking in the upconversion luminescence of thousands of lanthanide ions within a single nanocrystal. The blinking exhibits on-off intensity ratio exceeding 10, persists for over 15 hours (over 10,000 cycles) without discernible photodegradation, and can be reversibly controlled by adjusting the excitation power. We elucidate a universal, activator-independent upconversion blinking mechanism, whereby a single quencher, stochastically generated via a cooperative multi-ion process, can intercept delocalized excitation energy within the Yb3+ sensitizer network and darken the whole nanocrystal. Benefiting from the high-contrast, long-term photostable blinking and background-free emission, we achieve robust super-resolution localization microscopy that resolves individual nanocrystals in aggregates with 1.2 nm precision. This work establishes a general strategy to realize and control collective blinking in photostable multi-emitter nanosystems, opening new opportunities in nanoscience, bioimaging, and quantum technologies.