Wavelength dispersion of the local field intensity in silver-gold nanocages.

This study provides a combined theoretical and experimental analysis of the far-field (extinction) and of the near-field (SERS enhancement) spectral distribution in hollow nanoparticles, that is, silver-gold nanocages (NCs). Chitosan protected NCs have been synthesized by a galvanic replacement-based procedure: their morphological properties and chemical composition have been characterized by TEM, STEM and ICP. NCs were then functionalized with a thiolated organic dye prior to carrying out SERS measurements. Finite Element Method simulations of a single NC have shown that the field enhancement at the excitation wavelength follows the same spectral dependence as the extinction spectrum and, consequently, the SERS enhancement profile, as a function of the excitation wavelength, peaks at higher energy with respect to extinction. The simulated extinction is remarkably narrower than the experimental spectrum of NCs in solution, indicating that the colloidal sample is substantially polydispersed. However, a simple qualitative model that we have developed would suggest that the SERS enhancement profile is blue-shifted with respect to the extinction in the presence of polydispersivity as well. In addition, NC dimers have been simulated: both their extinction and near field-spectra shift to the red when the size of the gap is reduced analogous to what happens with dimers of filled spherical nanoparticles (NPs). In addition, simulations also revealed that a NC dimer is only slightly more efficient in amplifying the field with respect to the isolated NC, and this behavior is peculiar to NCs. In fact, filled spherical NP dimers exhibit a remarkably stronger field enhancement with respect to the isolated NP. By means of Wavelength Scanned SERS, we measured the spectral distribution of the local field in a dispersion of NCs. We observed experimentally that the local field is distributed in the same spectral region as the extinction and that the absolute value of the SERS enhancement factor maintains a low value throughout the range explored (568-800 nm). We propose that the observed correlation between the SERS profile and the extinction is accidental and originates from the limited increase in amplification provided by NC aggregates with respect to isolated NCs.

Preparation of small size palladium nanoparticles by picosecond laser ablation and control of metal concentration in the colloid.

We assessed a method for the preparation of small, highly stable and unprotected Pd nanoparticles by picosecond laser ablation in 2-propanol. The nanoparticles can be extracted from 2-propanol by centrifugation and redispersed in water, where a strongly negative ζ-potential assures long term stability. The proposed procedure permits reduction of particle size down to 1.6nm and optimization of the Pd(0):Pd(II) ratio which, in the best cases, was of the order of 6:1. The increase of this ratio with ablation times has been correlated to the high temperature conversion of PdO to metallic Pd by a simple theoretical model. A study of the relationship between colloid absorption at 400nm and Pd concentration permitted the role of PdO in the determination of the UV-vis spectra to be clarified and the limits of the Mie theory for the evaluation of colloid concentration to be established. The absorption at 400nm can be used as a fast method to estimate the Pd content in the colloids, provided that a calibration of the ablation process is preliminarily performed.

Functionalized Au/Ag nanocages as a novel fluorescence and SERS dual probe for sensing.

We obtained chitosan-protected Au/Ag nanocages (NCs), i.e., hollow and porous metallic nanoparticles, by galvanic replacement reaction. Subsequently, we functionalized the NCs with a fluorescent derivative of 4-methoxy-1,8-naphtalimide (NAFTA6). The plasmonic properties of these structures, which exhibit an extinction maximum in the 700-800 nm range, allowed their use as SERS active substrates for excitation at 785 nm and an efficient identification of the vibrational bands of NAFTA6, in spite of the low ligand concentration (<10(-5) M). Furthermore, NAFTA6 could also be identified from its fluorescence emission. The proposed functionalization with fluorescent compounds opens the way to the application of metal NCs using double-wavelength detection. Namely, Raman spectroscopy in the near infrared and fluorescence emission in the visible region, with considerable potential especially for in vivo medical applications, as the plasmonic band is centered in the visible light region where biological fluids and tissues are transparent.

All optical switches based on the coupling of surface plasmon polaritons.

We studied the potentials of All Optical Switches (AOS) based on the intensity-dependent coupling and decoupling of light into the SPP modes (Surface Plasmon Polaritons) of a sinusoidally corrugated thin metal film (TMF), due to Kerr induced refractive index changes of the surrounding dielectrics. The ideal device has two spatially separated outputs, collecting the reflected and transmitted light and the active volume can be as small as 10(-2) mm(3). Gold and PTS (poly-(2,4-hexadiyne-1,6-diol bis(p-toluene sulfonate) are the materials considered. Losses are limited to 1.5 dB,while a 20 dB extinction ratio per gate has been theoretically demonstrated with signal pulsewidths of 5-10 ps , using a maximum optical switching peak power of 11 kW.

Second harmonic generation from radiation to guided modes for the characterization of reverse-proton-exchanged waveguides.

By prism-coupling an ordinary radiation mode into a lithium niobate planar waveguide, a second harmonic extraordinary guided mode can be generated if the proper coupling angle is chosen. By measuring this angle, the effective index of the radiation mode and thus of the interacting guided mode can be determined. This fact is exploited for the characterization of reverse-proton-exchanged waveguides, whose lowest order modes cannot be efficiently prism-coupled due to their confinement inside the sample.

Photobleaching of polydiacetylene waveguides: a characterization of the process and patterning of optical elements.

The photobleaching process of poly-3butoxyl-carbonyl-methyl-urethane (poly-3BCMU) waveguides by means of an UV lamp and the 488-nm line of an Ar laser is characterized and modeled. The limits of the theory are discussed in light of experimental results, and we stress the role of the oxygen diffusion rate on the process. Finally, we adopt the photobleaching method to pattern a guided-wave micro-optic device and holographic diffraction gratings on spun poly-3BCMU films.

Thermal annealing of K(+)-Na(+) ion-exchanged waveguides.

The process of thermal annealing of K(+)(-)Na(+) ion-exchanged waveguides in soda lime glass is characterized and compared with a simple theoretical model. The discrepancies between theory and experiments in the case of initially thick guides disappear if the existence of a stress-induced contribution to the refractive index is assumed that is not proportional to the concentration of the doping ions. The results obtained for initially thin guides are exploited for the design of annealed single-mode channel waveguides: 0.4-dB coupling losses with commercial single-mode fibers at lambda = 1.321 microm were measured.