Tuning and Locking the Localized Surface Plasmon Resonances of CuS (Covellite) Nanocrystals by an Amorphous CuPdxS Shell

We demonstrate the stabilization of the localized surface plasmon resonance (LSPR) in a semiconductor-based core–shell heterostructure made of a plasmonic CuS core embedded in an amorphous-like alloyed CuPdxS shell. This heterostructure is prepared by reacting the as-synthesized CuS nanocrystals (NCs) with Pd2+ cations at room temperature in the presence of an electron donor (ascorbic acid). The reaction starts from the surface of the CuS NCs and proceeds toward the center, causing reorganization of the initial lattice and amorphization of the covellite structure. According to density functional calculations, Pd atoms are preferentially accommodated between the bilayer formed by the S–S covalent bonds, which are therefore broken, and this can be understood as the first step leading to amorphization of the particles upon insertion of the Pd2+ ions. The position and intensity in near-infrared LSPRs can be tuned by altering the thickness of the shell and are in agreement with the theoretical optical simulation based on the Mie–Gans theory and Drude model. Compared to the starting CuS NCs, the amorphous CuPdxS shell in the core–shell nanoparticles makes their plasmonic response less sensitive to a harsh oxidation environment (generated, for example, by the presence of I2)