Impact of supporting nanometric membranes on the thermo-optical dynamics of individual plasmonic nanodisks.

The thermal dynamics and transient optical response of individual gold nanodisks supported on thin silicon nitride membranes were investigated using optical time-resolved pump-probe spectroscopy and finite-element modeling. The effect of reducing the membrane thickness from 50 nm to 15 nm on the nanodisk thermal dynamics was explored. A significant deceleration of the nanodisk cooling kinetics was observed, and linked to a quasi-two-dimensional heat diffusion process within the 15 nm thick membrane, without detectable modification of its thermal conductivity.

Cooling Dynamics of Individual Gold Nanodisks Deposited on Thick Substrates and Nanometric Membranes.

The cooling dynamics of individual gold nanodisks synthesized using colloidal chemistry and deposited on solid substrates with different compositions and thicknesses were investigated using optical time-resolved spectroscopy and finite-element modeling. Experiments demonstrate a strong substrate-dependence of these cooling dynamics, which require the combination of heat transfer at the nanodisk/substrate interface and heat diffusion in the substrate. In the case of nanodisks deposited on a thick sapphire substrate, the dynamics are found to be mostly limited by the thermal resistance of the gold/sapphire interface, for which a value similar to that obtained in the context of previous experiments on sapphire-supported single gold nanodisks produced by electron beam lithography is deduced.

Ultrafast nano generation of acoustic waves in water via a single carbon nanotube.

Generation of ultra high frequency acoustic waves in water is key to nano resolution sensing, acoustic imaging and theranostics. In this context water immersed carbon nanotubes (CNTs) may act as an ideal optoacoustic source, due to their nanometric radial dimensions, peculiar thermal properties and broad band optical absorption. The generation mechanism of acoustic waves in water, upon excitation of both a single-wall (SW) and a multi-wall (MW) CNT with laser pulses of temporal width ranging from 5 ns down to ps, is theoretically investigated via a multiscale approach.

Versatile template-directed synthesis of gold nanocages with a predefined number of windows.

Highly symmetrical gold nanocages can be produced with a controllable number of circular windows of either 2, 3, 4, 6 or 12 via an original fabrication route. The synthetic pathway includes three main stages: the synthesis of silica/polystyrene multipod templates, the regioselective seeded growth of a gold shell on the unmasked part of the silica surface and the development of gold nanocages by dissolving/etching the templates. Electron microscopy and tomography provide evidence of the symmetrical features of the as-obtained nanostructures.

Signatures of Small Morphological Anisotropies in the Plasmonic and Vibrational Responses of Individual Nano-objects.

The plasmonic and vibrational properties of single gold nanodisks patterned on a sapphire substrate are investigated via spatial modulation and pump-probe optical spectroscopies. The features of the measured extinction spectra and time-resolved signals are highly sensitive to minute deviations of the nanodisk morphology from a perfectly cylindrical one. An elliptical nanodisk section, as compared to a circular one, lifts the degeneracy of the two nanodisk in-plane dipolar surface plasmon resonances, which can be selectively excited by controlling the polarization of the incident light.

Ultrafast electron-lattice thermalization in copper and other noble metal nanoparticles.

Using time-resolved ultrafast pump-probe spectroscopy we investigated the electron-lattice energy transfer in small copper nanospheres with diameters ranging from 3.2 to 23 nm, either embedded in a glass or dispersed in a solvent. Electron-lattice scattering rate is shown to increase with size reduction, in agreement with our previous results obtained on gold and silver nanoparticles in the low excitation regime.

High-Pressure Effect on the Optical Extinction of a Single Gold Nanoparticle.

When reducing the size of a material from bulk down to nanoscale, the enhanced surface-to-volume ratio and the presence of interfaces make the properties of nano-objects very sensitive not only to confinement effects but also to their local environment. In the optical domain, the latter dependence can be exploited to tune the plasmonic response of metal nanoparticles by controlling their surroundings, notably applying high pressures. To date, only a few optical absorption experiments have demonstrated this feasibility, on ensembles of metal nanoparticles in a diamond anvil cell.

Mechanical Vibrations of Atomically Defined Metal Clusters: From Nano- to Molecular-Size Oscillators.

Acoustic vibrations of small nanoparticles are still ruled by continuum mechanics laws down to diameters of a few nanometers. The elastic behavior at lower sizes (<1-2 nm), where nanoparticles become molecular clusters made by few tens to few atoms, is still little explored. The question remains to which extent the transition from small continuous-mass solids to discrete-atom molecular clusters affects their specific low-frequency vibrational modes, whose period is classically expected to linearly scale with diameter.

Controlling the Quality Factor of a Single Acoustic Nanoresonator by Tuning its Morphology.

The mechanical vibrations of individual gold nanodisks nanopatterned on a sapphire substrate are investigated using ultrafast time-resolved optical spectroscopy. The number and characteristics of the detected acoustic modes are found to vary with nanodisk geometry. In particular, their quality factors strongly depend on nanodisk aspect ratio (i.

Acoustic Mode Hybridization in a Single Dimer of Gold Nanoparticles.

The acoustic vibrations of single monomers and dimers of gold nanoparticles were investigated by measuring for the first time their ultralow-frequency micro-Raman scattering. This experiment provides access not only to the frequency of the detected vibrational modes but also to their damping rate, which is obscured by inhomogeneous effects in measurements on ensembles of nano-objects. This allows a detailed analysis of the mechanical coupling occurring between two close nanoparticles (mediated by the polymer surrounding them) in the dimer case.

Linear and ultrafast nonlinear plasmonics of single nano-objects.

Single-particle optical investigations have greatly improved our understanding of the fundamental properties of nano-objects, avoiding the spurious inhomogeneous effects that affect ensemble experiments. Correlation with high-resolution imaging techniques providing morphological information (e.g.

Fano Interference in the Optical Absorption of an Individual Gold-Silver Nanodimer.

Fano resonances are central features in the responses of many systems including atoms, molecules, and nanomaterials. They arise as a consequence of interferences between two channels, most frequently associated with two system modes. In plasmonic materials, Fano interferences between optical modes have been shown, experimentally and theoretically, to induce narrow features in their scattering spectra.

Optical absorption and scattering spectroscopies of single nano-objects.

Developments of optical detection and spectroscopy methods for single nano-objects are key advances for applications and fundamental understanding of the novel properties exhibited by nanosize systems. These methods are reviewed, focusing on far-field optical approaches based on light absorption and elastic scattering. The principles of the main linear and nonlinear methods are described and experimental results are illustrated in the case of metal nanoparticles, stressing the key role played by the object environment, such as the presence of a substrate, bound surface molecules or other nano-objects.

Time-domain investigation of the acoustic vibrations of metal nanoparticles: size and encapsulation effects.

The acoustic vibrations of single-metal and multi-material nanoparticles are studied by ultrafast pump-probe optical spectroscopy and described in the context of the continuous elastic model. The applicability of this model to the small size range, down to one nanometer, is discussed in the light of recent experimental data and ab initio calculations. Investigations of multi-material nano-objects stress the impact of the intra-particle interface on the characteristics of their vibrational modes, also yielding information on the composition and spatial distribution of the constituting materials.

Size-dependent surface plasmon resonance broadening in nonspherical nanoparticles: single gold nanorods.

The dependence of the spectral width of the longitudinal localized surface plasmon resonance (LSPR) of individual gold nanorods protected by a silica shell is investigated as a function of their size. Experiments were performed using the spatial modulation spectroscopy technique that permits determination of both the spectral characteristics of the LSPR of an individual nanoparticle and its morphology. The measured LSPR is shown to broaden with reduction of both the nanorod length and its diameter, which is in contrast with the predictions of existing classical and quantum theoretical models.

Optical response of individual Au-Ag@SiO₂ heterodimers.

The optical extinction response of individual Au-Ag@SiO2 heterodimers whose individual morphologies are determined by transmission electron microscopy (TEM) is investigated using spatial modulation spectroscopy. The extinction spectra show two resonances spectrally close to the surface plasmon resonances of the constituting Au and Ag@SiO2 core-shell particles. The interparticle electromagnetic coupling is demonstrated to induce a large increase of the optical extinction of the dimer around its Au-like surface plasmon resonance for light polarized along its axis, as compared to that for perpendicular polarization and to that of an isolated Au nanoparticle.

Damping of the acoustic vibrations of a suspended gold nanowire in air and water environments.

The lifetimes of the acoustic vibrations of metal nanostructures depend sensitively on the properties of the environment, such as the acoustic impedance and viscosity. In order to accurately study these effects, they have to be separated from the damping processes that are inherent to the nanostructure. Here we show that this can be done experimentally by investigating individual gold nanowires suspended over a trench in air and liquid environments.

A quantitative study of the environmental effects on the optical response of gold nanorods.

The effects of the dielectric environment on the optical extinction spectra of gold nanorods were quantitatively studied using individual bare and silica-coated nanorods. The dispersion and amplitude of their extinction cross-section, dominated by absorption for the investigated sizes, were measured using spatial modulation spectroscopy (SMS). The experimental results were compared to calculations from a numerical model that included environmental features present in the measurements and the morphology and size of the corresponding nanorods measured by transmission electron microscopy.

Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture.

Acoustic Vibrations in Bimetallic Au@Pd Core-Shell Nanorods.

The acoustic vibrations of gold nanorods coated with palladium were investigated as a function of Pd amount using ultrafast pump-probe spectroscopy. Both the extensional and breathing vibrational modes of the nanorods were coherently excited and detected. This permits precise determination of their periods, which were found to decrease and increase with Pd deposition, for the extensional and vibrational modes, respectively.

Surface plasmon resonance properties of single elongated nano-objects: gold nanobipyramids and nanorods.

The spectral characteristics (wavelength and line width) and the optical extinction cross-section of the longitudinal localized surface plasmon resonance (LSPR) of individual gold nanobipyramids have been quantitatively measured using the spatial modulation spectroscopy technique. The morphology of the same individual nanoparticles has been determined by transmission electron microscopy (TEM). The experimental results are thus interpreted with a numerical model using the TEM measured sizes of the particles as an input, and either including the substrate or assuming a mean homogeneous environment.

Acoustic vibrations of metal-dielectric core-shell nanoparticles.

The acoustic vibrations of metal nanoparticles encapsulated in a dielectric shell (Ag@SiO(2)) were investigated using a time-resolved femtosecond technique. The measured vibration periods significantly differ from those predicted for the bare metal cores and, depending on the relative core and shell sizes, were found to be either larger or smaller than them. These results show that the vibration of the whole core-shell particle is excited and detected.

Cellular strategies for regulating DNA supercoiling: a single-molecule perspective.

Entangling and twisting of cellular DNA (i.e., supercoiling) are problems inherent to the helical structure of double-stranded DNA.

Probing elasticity at the nanoscale: Terahertz acoustic vibration of small metal nanoparticles.

The acoustic response of surface-controlled metal (Pt) nanoparticles is investigated in the small size range, between 1.3 and 3 nm (i.e.

Anisotropy effects on the time-resolved spectroscopy of the acoustic vibrations of nanoobjects.

The impact of spherical symmetry breaking and crystallinity on the response of the vibrational acoustic modes of a nanoobject in frequency- and time-domain experiments is investigated using the finite-element analysis method. The results show that introduction of shape anisotropy, i.e.