Single-molecular spectroscopy reveals that photoluminescence (PL) of a single quantum dot blinks, randomly switching between bright and dim/dark states under constant photoexcitation, and quantum dots photobleach readily. These facts cast great doubts on potential applications of these promising emitters. After ∼20 years of efforts, synthesis of nonblinking quantum dots is still challenging, with nonblinking quantum dots only available in red-emitting window. Here we report synthesis of nonblinking quantum dots covering most part of the visible window using a new synthetic strategy, i.e., confining the excited-state wave functions of the core/shell quantum dots within the core quantum dot and its inner shells (≤ ∼5 monolayers). For the red-emitting ones, the new synthetic strategy yields nonblinking quantum dots with small sizes (∼8 nm in diameter) and improved nonblinking properties. These new nonblinking quantum dots are found to be antibleaching. Results further imply that the PL blinking and photobleaching of quantum dots are likely related to each other.

Transition metal doped semiconductor nanocrystals (d-dots) possess fundamentally different emission properties upon photo- or electroexcitation, which render them as unique emitters for special applications. However, in comparison with intrinsic semiconductor nanocrystals, the potential of d-dots has been barely realized, because many of their unique emission properties mostly rely on precise control of their photoluminescence (PL) decay dynamics. Results in this work revealed that it would be possible to obtain bright d-dots with nearly single-exponential PL decay dynamics. By tuning the number of Mn2+ ions per dot from ∼500 to 20 in Mn2+ doped ZnSe nanocrystals (Mn:ZnSe d-dots), the single-exponential PL decay lifetime was continuously tuned from ∼50 to 1000 μs. A synthetic scheme was further developed for uniform and epitaxial growth of thick ZnS shell, ∼7 monolayers. The resulting Mn:ZnSe/ZnS core/shell d-dots were found to be essential for necessary environmental durability of the PL properties, both steady-state and transient ones, for the d-dot emitters. These characteristics combined with intense absorption and high PL quantum yields (70 ± 5%) enabled greatly simplified schemes for various applications of PL lifetime multiplexing using Mn:ZnSe/ZnS core/shell d-dots.

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.

Here we report the first series of phase-pure zinc-blende CdSe/CdS core/shell quantum dots (QDs) with reproducibly controlled shell thickness (4–16 monolayers), which are nonblinking (≥95% ‘on’ time) in single-exciton regime for the entire series. These unique QDs possess well-controlled yet simple excited-state decay dynamics at both single-dot and ensemble levels, extremely small nonblinking volume threshold, if any, and unique ‘on’ and ‘off’ probability statistics. The outstanding optical properties of the QDs at the single-dot level were found to be correlated well with their ensemble properties. These small and bright nonblinking QDs offer promising technical application prospect in both single-dot and ensemble levels. The consistent and reproducible experimental results shed new light on the mechanisms of blinking of QDs.

Nearly monodisperse zinc-blende CdSe/CdS core/shell nanocrystals were synthesized by epitaxial growth of 1–6 monolayers of CdS shell onto presynthesized zinc-blende CdSe core nanocrystals in one pot. To retain the zinc-blende structure, the reaction temperature was lowered to the 100–140 °C range by using cadmium diethyldithiocarbamate as a single-source precursor and primary amine as activation reagents for the precursor. Although the wurtzite counterparts grown under the same conditions showed optical properties similar to those reported in the literature, zinc-blende CdSe/CdS core/shell nanocrystals demonstrated surprisingly different optical properties, with ensemble single-exponential photoluminescence decay, significant decrease of photoluminescence peak width by the shell growth, and comparatively high photoluminescence quantum yields. The lifetime for the single-exponential ensemble photoluminescence decay of zinc-blende CdSe/CdS core/shell nanocrystals with 3–4 monolayers of CdS shell was reproducibly found to be approximately 16.5 ± 1.0 ns.