Plasmon Modes Induced by Anisotropic Gap Opening in Au@Cu2O Nanorods

Integration of semiconductors with noble metals to form heteronanostructures can give rise to many interesting plasmonic and electronic properties. A number of such heteronanostructures have been demonstrated comprising noble metals and n‐type semiconductors, such as TiO₂, ZnO, SnO₂, Fe₃O₄, and CuO. In contrast, reports on heteronanostructures made of noble metals and p‐type semiconductors are scarce. Cu₂O is an unintentional p‐type semiconductor with unique properties. Here, the uniform coating of Cu₂O on two types of Au nanorods and systematic studies of the plasmonic properties of the resultant core–shell heteronanostructures are reported. One type of Au nanorods is prepared by seed‐mediated growth, and the other is obtained by oxidation of the as‐prepared Au nanorods. The (Au nanorod)@Cu₂O nanostructures produced from the as‐prepared nanorods exhibit two transverse plasmon peaks, whereas those derived from the oxidized nanorods display only one transverse plasmon peak. Through electrodynamic simulations the additional transverse plasmon peak is found to originate from a discontinuous gap formed at the side of the as‐prepared nanorods. The existence of the gap is verified and its formation mechanism is unraveled with additional experiments. The results will be useful for designing metal–semiconductor heteronanostructures with desired plasmonic properties and therefore also for exploring plasmon‐enhanced applications in photocatalysis, solar‐energy harvesting, and biotechnologies.