Selective Cation Exchange Enabled Growth of Lanthanide Core/Shell Nanoparticles with Dissimilar Structure

Core/shell nanostructure is versatile for improving or integrating diverse functions, yet it is still limited to homeomorphism with isomorphic core and shell structure. Here, we delineate a selective cation exchange strategy to construct lanthanide core/shell nanoparticles with dissimilar structure. Hexagonal NaLnF₄, a typical photon conversion material, was selected to grow cubic CaF₂ shell to protect surface exposed Ln³⁺. Preferential cation exchange between Ca²⁺ and Na⁺ triggered the surface hexagonal-to-cubic structure evolution, which remediated the large barrier for heteroepitaxy of monocrystalline CaF₂ shell. The heterostructured CaF₂ shell leads to greatly enhanced upconversion emission with increased absolute quantum yield from 0.2% to 3.7%. Moreover, it is advantageous in suppressing the interfacial diffusion of Ln³⁺, as well as the leakage of Ln³⁺ from nanoparticle to aqueous system. These findings open up a new avenue for fabricating heterostructured core/shell nanoparticles, and are instructive for modulating various properties.