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Colloidal solutions of gold nanorods and silver-coated gold nanorods were prepared. The seeded growth synthesis protocols were improved by adding a flocculation purification step. The resulting populations of pure gold nanorods and Au@Ag core–shell cuboids were characterized by very low dispersion in size and shape. UV–vis–near-infrared absorption measurements were performed on several batches of well-calibrated nano-objects, supported by calculations based on the discrete dipole approximation, allowed to highlight the impact of various morphological features on the optical response. In addition to the well-known effect of the nanorod aspect ratio on the shift of the longitudinal surface plasmon resonance mode, special attention was paid to changing either the rounding of the nanorod end-caps or that of the edges of the coating silver shell. Nanorods and cuboids were modeled as superellipsoids. This approach enabled us to model precisely their complex shapes using just a few simple parameters and analyze the evolution of their extinction spectra as a function of the rounding of their tips and edges. Such nano-objects are widely used for various applications in fields such as biomedical, biosensing, or surface-enhanced Raman spectroscopy, thus making it crucial to precisely assess the impact of each morphological feature for optimizing their performance. [ABSTRACT FROM AUTHOR]

The absorption spectra of 5 nm noble metal nanoparticles (Ag, Au, and Cu) with typical morphologies of multiply twinned particles (MTPs) and single crystals are calculated by using the discrete dipole approximation method. Among the considered morphologies, it is found that icosahedral, cuboctahedral and truncated octahedral particles behave like quasispherical particles whereas the optical response of the decahedral particles significantly differs from the others. This result, which originates from the shape anisotropy of the decahedron, points out the capacity to discriminate decahedral MTPs from a population of particles with mixed crystallinities and related quasispherical shapes. [ABSTRACT FROM AUTHOR]

Au nanoparticles (NPs) characterized by distinct surface chemistry (including dodecanethiol or oleylamine as capping agent), different sizes (∼5 and ∼10 nm) and crystallinities (polycrystalline or single crystalline), were chosen as seeds to demonstrate the versatility and robustness of our two-step core-shell Au@Ag NP synthesis process. The central component of this strategy is to solubilize the shell precursor (AgNO 3 ) in oleylamine and to induce the growth of the shell on selected seeds under heating. The shell thickness is thus controlled by the temperature, the annealing time, the (shell precursor)/(seed) concentration ratio, seed size and crystallinity. The shell thickness is thus shown to increase with the reactant concentration and to grow faster on polycrystalline seeds. The crystalline structure and chemical composition were characterized by HRTEM, STEM-HAADF, EELS and Raman spectroscopy. The plasmonic response of Au@Ag core-shell NPs as a function of core size and shell thickness was assessed by spectrophotometry and simulated by calculations based on the discrete dipole approximation (DDA) method. Finally, the nearly monodisperse core-shell Au@Ag NPs were shown to form micrometer-scale facetted 3D fcc-ordered superlattices (SLs) after solvent evaporation and deposition on a solid substrate. These SLs are promising candidates for applications as a tunable surface-enhanced Raman scattering platform.