Tuning infrared plasmon resonances in doped metal-oxide nanocrystals through cation-exchange reactions

Metal-oxide nanocrystals doped with aliovalent atoms can exhibit tunable infrared localized surface plasmon resonances (LSPRs). Yet, the range of dopant types and concentrations remains limited for many metal-oxide hosts, largely because of the difficulty in establishing reaction kinetics that favors dopant incorporation by using the co-thermolysis method. Here we develop cation-exchange reactions to introduce p-type dopants (Cu⁺, Ag⁺, etc.) into n-type metal-oxide nanocrystals, producing programmable LSPR redshifts due to dopant compensation. We further demonstrate that enhanced n-type doping can be realized via sequential cation-exchange reactions mediated by the Cu⁺ ions. Cation-exchange transformations add a new dimension to the design of plasmonic nanocrystals, allowing preformed nanocrystals to be used as templates to create compositionally diverse nanocrystals with well-defined LSPR characteristics. The ability to tailor the doping profile postsynthetically opens the door to a multitude of opportunities to deepen our understanding of the relationship between local structure and LSPR properties.