We report on the identification of surface plasmons in individual gold dumbbell-shaped nanoparticles (AuDBs), as well as AuDBs coated with silver. We use spatially resolved electron energy-loss spectroscopy in a scanning electron microscope, which allows us to map plasmon-energy and intensity spatial distributions. Two dominant plasmon resonances are experimentally resolved in both AuDBs and silver-coated AuDBs. The intensity of these features is peaked either at the tips or at the sides of the nanoparticles. We present boundary element method simulations in good agreement with the experiment, allowing us to elucidate the nature of such modes. While the lower-energy, tip-focused plasmon is of longitudinal character for all dumbbells under consideration, the second side-bound plasmon has a more involved symmetry, starting as a longitudinal quadrupole in homogeneous AuDBs and picking up transversal components when silver coating is added. The longitudinal dipolar mode energy is found to blue-shift upon coating with silver. We find that the substrate produces sizable shifts in the plasmons of silver-coated AuDBs. Our analysis portraits a complex plasmonic scenario in metal nanoparticles coated with silver, including a transition from the original homogeneous gold dumbbell plasmons to the modes of homogeneous silver rods. We believe that these findings can have potential application to plasmon engineering.
We have studied how spherical 23 ± 3 nm Au(45)Ag(55) nanoparticles embedded within a silica matrix transform into prolate nanorods and nanowires by irradiating them with swift heavy ions. Samples were irradiated at room temperature and normal incidence with 74 MeV Kr and 36 MeV S ions for fluences up to 1.0 × 10(15) cm(-2). We demonstrate the existence of two regimes: (i) below a critical fluence, ∼ 2.0 × 10(14) cm(-2), the transformation of the spherical nanoparticle into a nanorod is an individual process, i.e. each nanoparticle transforms into a single nanorod; (ii) for larger fluences the transformation from nanorod to nanowire becomes a collective process, i.e. the break up and dissolution of unstable nanorods contribute to the growth of long nanowires. The passage from the first to the second regime can be interpreted in terms of a Rayleigh-like instability under irradiation. The latter becomes active when the diameter of the nanowire approaches its saturation width under irradiation. Furthermore, we show that the composition of the alloy is only slightly modified during the ion-shaping process. Finally, the energy and the fluence thresholds for deformation and the deformation strain-rate are estimated.
We present the mapping of the plasmonic properties of gold nanoparticles that are embedded in a TiO2 thin film deposited over two different substrates, glass and silicon. An improved electron energy-loss spectroscopy (EELS) imaging technique was used to extract plasmon maps with nanometre resolution. Several representative cases of randomly dispersed NPs have been examined to carefully evaluate surrounding effects on the optical response of such nanostructured material. Data were compared to analytical calculations and showed good agreement. These results validate previous structural and far-field optical results and provide a clear description of the optical phenomena that take place at a nanometre scale in these materials. They are of primary importance for enlightening the way to the fabrication of thin film materials including metallic nanostructures for photovoltaic applications.
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