Insights on heterogeneity in blinking mechanisms and non-ergodicity using sub-ensemble statistical analysis of single...

Photo-luminescence (P-L) intermittency (or blinking) in semiconductor nanocrystals (NCs), a phenomenon ubiquitous to single-emitters, is generally considered to be temporally random intensity fluctuations between "bright" ("On") and "dark" ("Off") states. However, individual quantum-dots (QDs) rarely exhibit such telegraphic signals, and yet, a vast majority of single-NC blinking data are analyzed using a single fixed threshold which generates binary trajectories. Furthermore, while blinking dynamics can vary dramatically over NCs in the ensemble, the extent of diversity in the exponents (m_On/Off) of single-particle On-/Off-time distributions (P(t_On/Off)), often used to validate mechanistic models of blinking, remains unclear due to a lack of statistically relevant data sets. Here, we subclassify an ensemble of QDs based on the emissivity of each emitter and subsequently compare the (sub)ensembles' behaviors. To achieve this, we analyzed a large number (>1000) of blinking trajectories for a model system, Mn⁺² doped ZnCdS QDs, which exhibits diverse blinking dynamics. An intensity histogram dependent thresholding method allowed us to construct distributions of relevant blinking parameters (such as m_On/Off). Interestingly, we find that single QD P(t_On/Off)s follow either truncated power law or power law, and their relative proportion varies over subpopulations. Our results reveal a remarkable variation in m_On/Off amongst as well as within subensembles, which implies multiple blinking mechanisms being operational amongst various QDs. We further show that the m_On/Off obtained via cumulative single-particle P(t_On/Off) is distinct from the weighted mean value of all single-particle m_On/Off, evidence for the lack of ergodicity. Thus, investigation and analyses of a large number of QDs, albeit for a limited time span of a few decades, are crucial to characterize the spatial heterogeneity in possible blinking mechanisms.