Branched Heterostructured Semiconductor Nanocrystals with Various Branch Orders via a Facet-to-Facet Linking Process

Branched heterostructured semiconductor nanoparticles such as core seeded tetrapods and octapods offer properties not seen in their spherical core-shell counterparts, but are challenging to synthesize with a large diversity of branch numbers via heterogeneous nucleation and growth processes alone. This work describes a process to facet-link matchstick-like Ag₂S-tipped ZnS nanorods via their Ag₂S tips, producing branched Ag₂S-centered ZnS nanoparticles such as bipods, tripods, and in general multipods with 4 to 16 ZnS arms as a function of reaction time. The angle between nanorods in the bipods and tripods is found to be close to 120°, resulting in unexpected bent and trigonal planar geometry, respectively. This is attributed to the exposed facets of the monoclinic Ag₂S tips, their relative chemical reactivities, and their atomic composition. The formation of particles with an increasing number of branches takes place in a stepwise manner, thus making the facet-linking approach a facile synthesis route to systematically obtaining a diverse set of branched heterostructured semiconductor nanoparticles with a well-defined number of branches.