No abstract

Heterostructural core–shell quantum dots (hetero-QDs) have garnered a copious amount of research effort for not only scientific advances but also a range of technological applications. Particularly, controlling the heteroshell deposition, which in turn determines the particle morphology, is vital in regulating the photophysical properties and the application potential of the hetero-QDs. In this work, we present the first report on a synthesis of pyramidal shaped (i.e., hexagonal pyramid, HP, and hexagonal bipyramid, HBP) CdSe-CdS hetero-QDs with high morphological uniformity and epitaxial crystallinity through a two-step shell growth method. The stabilization of the exposed (0002) and {101̅1} facets by octadecylphosphonic acid and oleic acid ligands, respectively, is the key for the formation of pyramidal particle shapes. High photoluminescence quantum yield (94%, HP-QDs and 73%, HBP-QDs), minimal inhomogeneous PL line width broadening, and significantly suppressed single-QD blinking are observed. Specifically, the “giant” HBP-QDs showed an average “On” time fraction of 96% with more than 50% of measured particles completely nonblinking. Additionally, high multiexciton emission, prolonged ensemble and single-QD PL lifetimes as compared to their spherical counterparts are also reported. Finally, the HBP-QDs have been successfully transferred into an aqueous solution without aggregation. High cellular uptakes associated with low cytotoxicity render these water-soluble HBP-QDs an excellent candidate for intracellular imaging and labeling.

Research interest in dynamic assemblies of coordination polymers (CPs) has been rising in recent years for the similarity with life systems in their self-adaptable morphologies and properties. However, monitoring of the assembly process and elucidating the nature for the morphological transformation are very challenging. Here, UV-Vis spectroscopy has been explored as a time-resolved method for monitoring the self-assembly of Au(I)-thiolate CPs in situ. Both step-wise and synergetic effects of the weak interactions in Au(I)-3-mercaptopropionic acid (MPA) CPs, such as H-bonding, coordination bonding, Au(I)-Au(I) interactions and static interactions have been found from the spectral fingerprints, which elucidated the driving forces for the unique morphological transformations from strings to lamellar structures. This work represents a breakthrough in that dynamic self-assembly behaviours can be explained by molecular interactions from molecular level evidences. Based on the spectral fingerprint-structure relationship the reversible and dynamic assembly of Au(I)-MPA CPs can be easily probed.

Fabrication of quantum dots (QDs) with emission covering a wide spectral region has been persistently intriguing because of their potentials in a range of practical applications such as biological labeling and imaging, solar cells, light-emitting diodes, and next-generation displays. In this work, we report the synthesis of CdZnSe–CdZnS core–shell alloy QDs through a Cu-catalyzed solid solution alloying strategy starting from CdSe–CdS core–shell QDs. The resulting CdZnSe–CdZnS alloy QDs exhibit emission profiles covering a wide wavelength range of 470–650 nm while maintaining high photoluminescence quantum yields. In addition, high morphological uniformity of the starting CdSe–CdS QDs can be largely retained in the final alloy QDs. We attribute this alloying process to the high mobility nature of Cu cations in Cd-chalcogenide crystals at elevated reaction temperatures, which allows Cu cations to act as transporting agents to transfer a Zn component into the CdSe–CdS QDs while maintaining the particle integrity. We show that this unique alloying strategy is independent of the shape of the starting QDs and can also be applied to the synthesis of CdZnSe–CdZnS nanorods. We anticipate that our study will instigate the synthesis of various high-quality alloy QDs and other alloy nanocrystals beyond what can be achieved currently.

Hollow bimetallic nanostructures exhibit increased durability and utilization efficiency compared to their solid counterparts, and therefore have become promising new candidates for catalytic applications.