Robust raspberry-like metallo-dielectric nanoclusters of critical sizes as SERS substrates.

Raspberry-like nano-objects made of large plasmonic satellites (>10 nm) covering a central dielectric particle have many potential applications as photonic materials, superlenses and (bio-) sensors, but their synthesis remains challenging. Herein, we show how to build stable and robust raspberry-like nano-systems with close-packed satellites, by combining monodisperse silica particles (80 or 100 nm diameter) and oppositely charged noble metal nanoparticles (Au or Ag) with well-defined sizes (10-50 nm). The spectral characteristics of their associated plasmonic resonances (wavelength, linewidth, extinction cross-section) and the electromagnetic coupling between satellites were observed using the spatial modulation spectroscopy technique and interpreted through a numerical model. The composite nano-objects exhibit numerous hot spots at satellite junctions, resulting in excellent surface-enhanced Raman scattering (SERS) performance. The SERS efficiency of the raspberry-like clusters is highly dependent on their structure.

Ultrafast nonlinear optical response of a single gold nanorod near its surface plasmon resonance.

The ultrafast optical nonlinearity of an optically characterized single gold nanorod is investigated around its surface plasmon resonance, by combining a far-field spatial modulation technique with a high sensitivity pump-probe setup. The spectrally and temporally dependent response is quantitatively interpreted in terms of the bulklike optical nonlinearity enhanced by the plasmonic effect. The plasmon resonance dynamics is shown to be mostly governed by nonequilibrium electron and phonon processes. Their contributions to the nonlinear optical response of a single metal nano-object are elucidated, and the latter is connected to the nonlinearities of ensembles.

Quantitative determination of the size dependence of surface plasmon resonance damping in single Ag@SiO(2) nanoparticles.

The optical extinction spectra of single silver nanoparticles coated with a silica shell were investigated in the size range 10-50 nm. Measurements were performed using the spatial modulation spectroscopy technique which permits independent determination of both the size of the metal nanoparticle under study and the width of its localized surface plasmon resonance (LSPR). These parameters can thus be directly correlated at a single particle level for the first time. The results show a linear increase of the width of the LSPR with the inverse diameter in the small size regime (less than 25 nm). For these nanoparticles of well-controlled environment, this can be ascribed to quantum confinement of electrons or, classically, to increase of the electron surface scattering processes. The impact of this effect was measured quantitatively and compared to the predictions by theoretical models.

Fano profiles induced by near-field coupling in heterogeneous dimers of gold and silver nanoparticles.

The near-field coupling between a gold and a silver spherical nanoparticle is investigated theoretically. Fano profiles are observed in the absorption cross section of the gold nanoparticle due to the coupling between the spectrally localized surface plasmon resonance of the silver nanoparticle and the continuum of interband transitions of the gold one. The effect of dimer internal characteristics (particle sizes and distance), surrounding medium (through the refractive index), and external excitation (polarization and propagation directions) are addressed. In particular, it is shown that the near-field coupling can be tuned from the weak to the strong regime by rotating the polarization direction, and that the Fano profiles are sensitive to the shadowing effect even for small particle sizes.

Optical properties and relaxation processes at femtosecond scale of bimetallic clusters.

The optical properties of Au-Ag and Ni-Ag clusters are measured by linear optical absorption spectroscopy and the time-resolved pump-probe femtosecond technique allowing a study of the influence of alloy or core-shell structure.

Coherent acoustic vibration of metal nanoshells.

Using time-resolved pump-probe spectroscopy, we have performed the first investigation of the vibrational modes of gold nanoshells. The fundamental isotropic mode launched by a femtosecond pump pulse manifests itself in a pronounced time-domain modulation of the differential transmission probed at the frequency of nanoshell surface plasmon resonance. The modulation amplitude is significantly stronger, and the period is longer than that in a gold nanoparticle of the same overall size, in agreement with theoretical calculations. This distinct acoustical signature of nanoshells provides a new and efficient method for identifying these versatile nanostructures and for studying their mechanical and structural properties.

Optical control of the coherent acoustic vibration of metal nanoparticles.

Optical control of the coherent breathing vibrations of silver nanospheres is demonstrated using a high-sensitivity femtosecond pump-probe technique in a double-pump pulse configuration. Oscillation of the fundamental mode that usually dominates the time-domain vibrational response can thus be stopped, permitting observation of the first order radial mode and determination of its properties. These are found to be in agreement with the predictions of the model of an elastic sphere embedded in an elastic matrix.

Direct measurement of the single-metal-cluster optical absorption.

The absorption of a single isolated metal cluster is directly measured using a novel far-field optical technique based on modulation of its position. Single gold nanoparticles with average diameters down to 5 nm, dispersed on a transparent substrate, are optically detected and their absolute absorption cross section determined.

Size-dependent electron-electron interactions in metal nanoparticles

The internal thermalization dynamics of the conduction electrons is investigated in silver nanoparticles with radius ranging from 13 to 1.6 nm using a femtosecond IR pump-UV probe absorption saturation technique. A sharp increase of the electron energy exchange rate is demonstrated for nanoparticles smaller than 5 nm. The results are consistent with electron-electron scattering acceleration due to surface induced reduction of the Coulomb interaction screening by the conduction and core electrons.