Plasmon-enhanced multi-photon excited photoluminescence of Au, Ag, and Pt nanoclusters.

In this work, we have studied the multi-photon excited photoluminescence from metal nanoclusters (NCs) of Au, Ag and Pt embedded in Al2O3matrix by ion implantation. The thermal annealing process allows to obtain a system composed of larger plasmonic metal nanoparticles (NPs) surrounded by photoluminescent ultra-small metal NCs. By exciting at 1064 nm, visible emission, ranging from 450 to 800 nm, was detected. The second and fourth-order nature of the multiphoton process was verified in a power-dependent study measured for each sample below the damage threshold. Experiments show that Au and Ag NCs exhibit a four-fold enhanced multiphoton excited photoluminescence with respect to that observed for Pt NCs, which can be explained as a result of a plasmon-mediated near-field process that is of less intensity for Pt NPs. These findings provide new opportunities to combine plasmonic nanoparticles and photoluminescent nanoclusters inside a robust inorganic matrix to improve their optical properties. Plasmon-enhanced multiphoton excited photoluminescence from metal nanoclusters may find potential application as ultrasmall fluorophores in multiphoton sensing, and in the development of solar cells with highly efficient energy conversion modules.

Tuning the aspect ratio of silver nanospheroids embedded in silica: erratum.

We present a corrigendum to our Letter [Opt. Lett.35, 703 (2010)10.1364/OL.35.000703]. In the original Letter we inadvertently included in Fig. 2(a) a TEM micrograph corresponding to a different, but very similar, sample. This corrigendum replaces Fig. 2(a) with a correct version. Since the main results are rather based in optical absorption measurements, and their modeling by using the T-matrix method, this correction does not affect the results and conclusions of the original Letter.

Superlinear Photoluminescence by Ultrafast Laser Pulses in Dielectric Matrices with Metal Nanoclusters.

An intense photoluminescence emission was observed from noble metal nanoclusters (Pt, Ag or Au) embedded in sapphire plates, nucleated by MeV ion-implantation and assisted by an annealing process. In particular, the spectral photoluminescence characteristics, such as range and peak emission, were compared to the behavior observed from Pt nanoclusters embedded in a silica matrix and excited by UV irradiation. Correlation between emission energy, nanoclusters size and metal composition were analyzed by using the scaling energy relation EFermi/N1/3 from the spherical Jellium model. The metal nanocluster luminescent spectra were numerically simulated and correctly fitted using the bulk Fermi energy for each metal and a Gaussian nanoclusters size distribution for the samples. Our results suggest protoplasmonics photoluminescence from metal nanoclusters free of surface state or strain effects at the nanoclusters-matrix interface that can influence over their optical properties. These metal nanoclusters present very promising optical features such as bright visible photoluminescence and photostability under strong picosecond laser excitations. Besides superlinear photoluminescence from metal nanoclusters were also observed under UV high power excitation showing a quadratic dependence on the pump power fluence.

Nonlinear optical response of platinum nanoparticles and platinum ions embedded in sapphire.

We report on the fabrication of sapphire samples containing platinum nanoparticles (Pt-NPs) and platinum ions (Pt-ions) and the investigation of their third-order nonlinear (NL) optical properties. The presence of Pt-NPs was confirmed by electronic microscopy and by the linear absorption spectrum that shows a localized surface plasmon band centered at 290 nm. A sample without NPs but containing Pt-ions was also studied. The absorptive and refractive contributions to the nonlinearity were studied using the z-scan technique with 100 fs pulses at 800nm. The experiments revealed a NL refractive index, +3.8×10-13 < n2 < +1.3×10-12cm2/W and NL absorption coefficient (ß < 9.3 cm/GW). The results show enhancement of about five orders of magnitude with respect to the NL refractive index of sapphire.

Ultrafast optical phase modulation with metallic nanoparticles in ion-implanted bilayer silica.

The nonlinear optical response of metallic-nanoparticle-containing composites was studied with picosecond and femtosecond pulses. Two different types of nanocomposites were prepared by an ion-implantation process, one containing Au nanoparticles (NPs) and the other Ag NPs. In order to measure the optical nonlinearities, we used a picosecond self-diffraction experiment and the femtosecond time-resolved optical Kerr gate technique. In both cases, electronic polarization and saturated absorption were identified as the physical mechanisms responsible for the picosecond third-order nonlinear response for a near-resonant 532 nm excitation. In contrast, a purely electronic nonlinearity was detected at 830 nm with non-resonant 80 fs pulses. Regarding the nonlinear optical refractive behavior, the Au nanocomposite presented a self-defocusing effect, while the Ag one presented the opposite, that is, a self-focusing response. But, when evaluating the simultaneous contributions when the samples are tested as a multilayer sample (silica-Au NPs-silica-Ag NPs-silica), we were able to obtain optical phase modulation of ultra-short laser pulses, as a result of a significant optical Kerr effect present in these nanocomposites. This allowed us to implement an ultrafast all-optical phase modulator device by using a combination of two different metallic ion-implanted silica samples. This control of the optical phase is a consequence of the separate excitation of the nonlinear refracting phenomena exhibited by the separate Au and Ag nanocomposites.

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.

Thermo-optic effect and optical third order nonlinearity in nc-Si embedded in a silicon-nitride film.

Using a self-diffraction experiment with 7ns pulses at 532nm we studied a silicon nitride film containing silicon nanoclusters (nc-Si) of 3.1+/-0.37 nm mean size. The sample was prepared by remote plasma-enhanced chemical vapor deposition (RPECVD), and we found that its nonlinearity consists of a combination of electronic and thermal contributions. By varying the repetition rate of the laser, we discriminated the responsible mechanisms for the nonlinear response. Using this procedure we determined a total /chi((3))1111/ = 3.3x10(-10)esu, n2 = 2.7x10(-16) m(2)/W, beta = 1x10(-9) m/W and dn/dT =1x10(-4) degrees C(-1) for our sample. We also show results for the optical Kerr effect using 80 fs pulses at 820 nm. The purely electronic nonlinearity measured is characterized by /chi((3))1111/=9.5 x10(-11) esu.

Absorptive and refractive nonlinearities by four-wave mixing for Au nanoparticles in ion-implanted silica.

We report a theoretical and experimental study on the real and imaginary part of the third-order nonlinear optical susceptibility at 532 nm and 7 ns pulse for high-purity silica samples containing Au nanoparticles prepared by ion implantation. We present a method for measuring the magnitude and sign of refractive and absorptive nonlinearities based on four-wave mixing (FWM). This method is derived from a comparison of the light intensities of incident and self-diffracted polarized waves. In the nanosecond regime the samples exhibit saturable absorption and it seems that a thermal effect is the mechanism responsible of nonlinearity of index.