Local Plasmonic Studies on Individual Core–Shell Gold–Silver and Pure Gold Nano-Bipyramids

Bimetallic systems present new opportunities to tailor the optical properties of nanoparticles. Morphology, structural, and optical properties of gold and of gold–silver nanoparticles have been studied by three-dimensional (3D) scanning transmission electron microscopy (STEM), STEM imaging, and monochromated subnanometer electron beams. The 3D morphology of these nanoparticles consists of bipyramidal prisms with well-defined facets. Furthermore, in the case of the core–shell nanoparticles, from these tomographical studies, we have determined the silver (shell) distribution and their atomic arrangement. Multipolar localized surface plasmon resonances (LSPR) have been studied, at subnanometer level and at high-energy resolution, as a function of their shape, their size (aspect ratio), and the surrounding environment. These results have been interpreted in the framework of the discrete dipole approximation (DDA) simulations. The effect of the silver outer-shell has been elucidated. We observed a significant damping of plasmon excitations due to the difference of dielectric function of these two metals. In addition, we have shown that the combination of the tomographical and plasmonic (experiments and simulations) studies with such high spatial resolution constitutes a very powerful and fundamental tool for understanding and optimizing the photonics properties of nanomaterials