V. Rodríguez-Iglesias

Anisotropic linear and nonlinear optical properties from anisotropy-controlled metallic nanocomposites

High-energy metallic ions were implanted in silica matrices, obtaining spherical-like metallic nanoparticles (NPs) after a proper thermal treatment. These NPs were then deformed by irradiation with Si ions, obtaining an anisotropic metallic nanocomposite. An average large birefringence of 0.06 was measured for these materials in the 300-800 nm region. Besides, their third order nonlinear optical response was measured using self-diffraction and P-scan techniques at 532 nm with 26 ps pulses. By adjusting the incident lights polarization and the angular position of the nanocomposite, the measurements could be directly related to, at least, two of the three linear independent components of its third order susceptibility tensor, finding a large, but anisotropic, response of around 10(-7) esu with respect to other isotropic metallic systems. For the nonlinear optical absorption, we were able to shift from saturable to reverse saturable absorption depending on probing the Au NPs major or minor axes, respectively. This fact could be related to local field calculations and NPs electronic properties. For the nonlinear optical refraction, we passed from self-focusing to self-defocusing, when changing from Ag to Au.

Determination of the size distribution of metallic nanoparticles by optical extinction spectroscopy

A method is proposed to estimate the size distribution of nearly spherical metallic nanoparticles (NPs) from optical extinction spectroscopy (OES) measurements based on Mies theory and an optimization algorithm. The described method is compared against two of the most widely used techniques for the task: transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS). The size distribution of Au and Cu NPs, obtained by ion implantation in silica and a subsequent thermal annealing in air, was determined by TEM, grazing-incidence SAXS (GISAXS) geometry, and our method, and the average radius obtained by all the three techniques was almost the same for the two studied metals. Concerning the radius dispersion (RD), OES and GISAXS give very similar results, while TEM considerably underestimates the RD of the distribution.

Tuning the aspect ratio of silver nanospheroids embedded in silica

A method is proposed to control the aspect ratio (epsilon) of elongated nanoparticles obtained by ion implantation in a transparent matrix. The procedure was tested for Ag spheroids in silica and we could accurately change epsilon in the range from the maximum value obtained by the ion implantation (around 3.0 in this case) to 1.0 (spherical shape). The values of epsilon were determined in several steps from optical extinction spectroscopy measurements, by fitting the modification and splitting of the surface plasmon resonance peak, using the T-matrix method. In the initial (maximum deformation) and final (undeformed) states, transmission electron microscopy images were obtained, showing a good agreement with the T-matrix results in both cases.

Near- and Far-Field Optical Response of Eccentric Nanoshells

We study the optical response of eccentric nanoshells (i.e., spherical nanoparticles with an eccentric spherical inclusion) in the near and the far field through finite-difference time-domain simulations. Plasmon hybridization theory is used to explain the obtained results. The eccentricity generates a far-field optical spectrum with various plasmon peaks. The number, position, and width of the peaks depend on the core offset. Near-field enhancements in the surroundings of these structures are significantly larger than those obtained for equivalent concentric nanoshells and, more importantly, they are almost independent of the illumination conditions. This opens up the door for using eccentric nanoshells in applications requiring intense near-field enhancements.

GISAXS Size Distribution Characterization of Cu Nanoparticles Embedded in silica

Cu nanoparticles embedded in high purity silica produced by deep ion implantation at 2 MeV and located around 0.8 μm underneath the surface were analyzed by GISAXS and TEM. Same results were obtained by both techniques, indicating that GISAXS is a reliable method for shape and size characterization of metallic nanoclusters underneath the surface of a silica matrix. The Cu nanoparticles presented a nearly‐spherical shape with a mean radius around 3±1.2 nm.