Ligand-induced chirality in asymmetric CdSe/CdS core–shell nanocrystals (NCs) has been extensively applied in chiral biosensors, regioselective syntheses and assemblies, circularly polarized luminescence (CPL), and chiroptic-based devices due to their excellent physiochemical properties, such as the tunable quantum confinement effects, surface functionality, and chemical stability. Herein, we present CdSe/CdS NCs with various morphologies such as nanoflowers, tadpoles, and dot/rods (DRs) with chirality induced by surface chiral ligands. The observed circular dichroism (CD) and CPL activities are closely associated with the geometrical characteristics of the nanostructures, such as the shell thickness and the aspect ratio of the CdSe/CdS NCs. Furthermore, in situ observations of the growth of tadpoles with a single tail indicate that the CD response is mainly attributed to the CdS shell, which has a maximum tail length of ∼45 nm (approximately λ/10 of the incident light wavelength). On the other hand, the CPL activity is only related to the CdSe core, and the activity benefits from a thin CdS shell with a relatively high photoluminescence quantum yield (QY). Further theoretical models demonstrated the aspect-ratio-dependent g-factor and QY variations in these asymmetric nanostructures. These findings provide insights into not only the asymmetric synthesis of CdSe/CdS NCs, but also the rational design of CdSe/CdS nanostructures with tunable CD and CPL activities.
Lv Bihu,Zhang Huichao,Wang Lipeng,Zhang Chunfeng,Wang Xiaoyong,Zhang Jiayu,Xiao Min
When closely packed into a high-density film, semiconductor nanocrystals (NCs) can interact with each other to yield collective optical behaviours, which are normally difficult to characterize due to the ensemble average effect. Here we synthesized semiconductor NC clusters and performed single-particle spectroscopic measurements to probe the electronic couplings of several giant CdSe/CdS NCs contained in one cluster with nanometer-scale separations. Such a single cluster exhibits multiple emission peaks at the cryogenic temperature with nearly identical photoluminescence decay dynamics, suggesting that the Förster-type energy transfer does not occur among the composing NCs. Surprisingly, strong photon antibunching is still observed from a single cluster, which can be attributed to the Auger annihilation of photo-excited excitons from different NCs. The isolation of several nearby NCs interacting with the above novel mechanism has marked a solid progress towards a full understanding and an efficient control of the operation parameters in NC-based optoelectronic devices.
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