Symmetry breaking in semiconductor nanocrystals via kinetic-controlled surface diffusion: a strategy for manipulating the junction structure

The synthesis of semiconductor nanocrystals is usually limited to high-level symmetry, as constrained by the inherent, for example, face-centered cubic or hexagonal close-packed lattices of the crystals. Herein, we report a robust approach for breaking the symmetry of the CdS lattice and obtaining high-quality CdS ultrathin monopods, bipods, tripods, and tetrapods. The success relies on manipulating reaction kinetics by dropwise addition of a precursor solution, which permits deterministic control over the number of CdS monomers in the reaction solution. With rapid monomer supply by fast precursor injection, growth was restricted to only one {111} facet of the nascent CdS tetrahedron to produce an asymmetric ultrathin monopod (a zinc-blende tip with a wurtzite arm). Otherwise, growth monomers could access adjacent {111} facets through surface diffusion and thus lead to the switch of the growth pattern from asymmetric to symmetric to generate an ultrathin multipod (a zinc-blende tip/core with multi-wurtzite arms). These symmetry-controlled photocatalysts were characterized by a fine-tuned zinc blende-wurtzite intergrowth type-II homojunction. After evaluating their structure-dependent solar-hydrogen-production properties, the CdS ultrathin monopod with an appropriate length for controllable charge transportation showed the highest photocatalytic activity.