Currently, the most common way to reduce blinking in quantum dots (QDs) is accomplished by using very thick and/or perfectly crystalline CdS shells on CdSe cores. Ideally, a nontoxic material such as ZnS is preferred to be the outer material in order to reduce environmental and cytotoxic effects. Blinking suppression with multishell configurations of CdS and ZnS has been reported only for "giant" QDs of 15 nm or more. One of the main reasons for the limited progress is that the role that interfacial trap states play in blinking in these systems is not very well understood. Here, we show a "Goldilocks" effect to reduce blinking in small (∼7 nm) QDs by carefully controlling the thicknesses of the shells in multishell QDs. Furthermore, by correlating the fluorescence lifetime components with the fraction of time that a QD spends in the on-state, both with and without applying a threshold, we found evidence for two types of blinking that separately affect the average fluorescence lifetime of a single QD. A thorough characterization of the time-resolved fluorescence at the ensemble and single-particle level allowed us to propose a detailed physical model involving both short-lived interfacial trap states and long-lived surface trap states that are coupled. This model highlights a strategy of reducing QD blinking in small QDs by balancing the magnitude of the induced lattice strain, which results in the formation of interfacial trap states between the inner shell and the outer shell, and the confinement potential that determines how accessible the interfacial trap states are. The combination of reducing blinking while maintaining a small overall QD size and using a Cd-free outer shell of ZnS will be useful in a wide array of applications, particularly for advanced bioimaging.

The majority of quantum dot (QD) blinking studies have used a model of switching between two distinct fluorescence intensity levels, "on" and "off". However, a distinct intermediate intensity level has been identified in some recent reports, a so-called "grey" or "dim" state, which has brought this binary model into question. While this grey state has been proposed to result from the formation of a trion, it is still unclear under which conditions it is present in a QD. By performing shell-dependent blinking studies on CdSe QDs, we report that the populations of the grey state and the on state are strongly dependent on both the shell material and its thickness. We found that adding a ZnS shell did not result in a significant population of the grey state. Using ZnSe as the shell material resulted in a slightly higher population of the grey state, although it was still poorly resolved. However, adding a CdS shell resulted in the population of a grey state, which depended strongly on its thickness up to 5 ML. Interestingly, while the frequency of transitions to and from the grey state showed a very strong dependence on CdS shell thickness, the brightness of and the dwell time in the grey state did not. Moreover, we found that the grey state acts as an on-pathway intermediate state between on and off states, with the thickness of the shell determining the transition probability between them. We also identified two types of blinking behavior in QDs, one that showed long-lived but lower intensity on states and another that showed short-lived but brighter on states that also depended on the shell thickness. Intensity-resolved single QD fluorescence lifetime analysis was used to identify the relationship between the various exciton decay pathways and the resulting intensity levels. We used this data to propose a model in which multiple on, grey, and off states exist whose equilibrium populations vary with time that give rise to the various intensity levels of single QDs and which depends on shell composition and thickness.

Choosing the composition of the shell for QDs is not trivial, since both the band-edge energy offset and interfacial lattice mismatch play roles in influencing the final optical properties. One way to balance these competing effects is by forming multi-shells and/or gradient-alloyed shells. However, this introduces multiple interfaces and their relative effects on quantum yield and blinking are not yet fully understood. Here we undertake a systematic, comparative study of adding inner shells of single composition vs gradient-alloyed shells of cadmium/zinc chalogenides onto CdSe cores, and then capping with a thin ZnS outer shell to form various core/multi-shell configurations. We show that the inner shell architecture between the CdSe core and the outer ZnS shell plays a significant role in both quantum yield and blinking dynamics but that these effects are not correlated – a high ensemble quantum yield doesn’t necessarily equate to reduced blinking. Two mathematical models have been proposed to describe the blinking dynamics – the more common power-law model and a more recent multi-exponential model. By binning the same data with 1 ms and 20 ms resolution, we show that the on-times can be better described by the multi-exponential model while the off-times can be better described by the power-law model. We discuss physical mechanisms that might explain this behavior and how it can be affected by the inner shell architecture.

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