Theoretical and time-domain experimental investigations of the vibrational acoustic response of nano-objects are described focusing on metallic ones. Acoustic vibrations are modeled using a ...macroscopic-like approach based on continuum mechanics with the proper boundary conditions, a model which yields results in excellent agreement with the experimental ones and those of atomistic calculations, down to the nanometric scale. Vibrational mode excitation and detection mechanisms and the associated mode selection in ultrafast pump–probe spectroscopy are discussed, and the measured time-dependent signals in single and ensemble of nanoparticles modeled. The launched modes, their period and their damping rate are compared to experimental results obtained on ensembles of nano-objects with different composition, morphology and environment, and with size ranging from one to hundreds of nanometers. Recent extension of time-domain spectroscopy to individual nano-objects has shed new light on the vibrational responses of isolated nanoparticles, in particular on their damping, but also raises questions on the origin of its large particle to particle dispersion.
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. Here, we investigate experimentally by ultrafast time-resolved optical spectroscopy the acoustic response of atomically defined ligand-protected metal clusters Au n (SR) m with a number n of atoms ranging from 10 to 102 (0.5–1.5 nm diameter range). Two periods, corresponding to fundamental breathing- and quadrupolar-like acoustic modes, are detected, with the latter scaling linearly with cluster diameters and the former taking a constant value. Theoretical calculations based on density functional theory (DFT) predict in the case of bare clusters vibrational periods scaling with size down to diatomic molecules. For ligand-protected clusters, they show a pronounced effect of the ligand molecules on the breathing-like mode vibrational period at the origin of its constant value. This deviation from classical elasticity predictions results from mechanical mass-loading effects due to the protecting layer. This study shows that clusters characteristic vibrational frequencies are compatible with extrapolation of continuum mechanics model down to few atoms, which is in agreement with DFT computations.
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. Experiments are performed using an optical time-resolved pump–probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron–hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron–hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal–semiconductor nanohybrids in light-harvesting applications and in photocatalysis.
The coupling effects affecting the vibrations of two close nanostructures (e.g., two metal nanoplates or nanospheres separated by a thin dielectric layer) may considerably alter their vibrational ...eigenfrequencies, as demonstrated by several recent experimental studies. In this work, we present theoretical investigations of these coupling processes based on a continuum mechanics approach, considering various systems composed by two identical nanostructures mechanically coupled by a spacer made of a different material and computing their eigenfrequencies as a function of the spacer thickness. We first discuss the vibrations of stacked slabs, a one-dimensional problem which can be treated analytically. The more complex configurations of dimers of rods or spheres coupled by a finite cylindrical spacer are then treated numerically. In all cases, the frequency shifts occurring for thin spacers can be simply interpreted as a modification of the boundary conditions of the problem as compared to the single nanostructure case, while those predicted near specific spacer thicknesses are ascribed to an avoided crossing effect, happening when the individual building blocks of the dimers (nanostructures and spacer) present common eigenfrequencies.
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.e., diameter over height ratio), reaching a maximal value of ≈70, higher than those previously measured for substrate-supported nano-objects. The peculiarities of the detected acoustic vibrations are confirmed by finite-element simulations, and interpreted as the result of substrate-induced hybridization between the vibrational modes of a nanodisk. The present findings demonstrate novel possibilities for engineering the vibrational modes of nano-objects.
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. For spherical particles, this interaction also leads to comparable shifts with light polarization of the two dimer resonances, an effect masked or even reversed for particles significantly deviating from sphericity. Both amplitude and spectral effects are found to be in excellent quantitative agreement with numerical simulations when using the TEM-measured dimer morphology (i.e., size, shape, and orientation of the individual dimers), stressing the importance of individual morphology characterization for interpreting heterodimer optical response.
The acoustic response of surface-controlled metal (Pt) nanoparticles is investigated in the small size range, between 1.3 and 3 nm (i.e., 75−950 atoms), using time-resolved spectroscopy. Acoustic ...vibration of the nanoparticles is demonstrated, with frequencies ranging from 1.1 to 2.6 THz, opening the way to the development of THz acoustic resonators. The frequencies, measured with a noncontact optical method, are in excellent agreement with the prediction of a macroscopic approach based on the continuous elastic model, together with the bulk material elastic constants. This demonstrates the validity of this model at the nanoscale and the weak impact of size reduction on the elastic properties of a material, even for nanoparticles formed by less than 100 atoms.
With the recent advances of experimental techniques, the nonlinear ultrafast optical response of metal nano-objects can now be investigated both on ensembles and on single nanoparticles. Its ...connection with the metal electronic and lattice kinetics is studied on the basis of a model describing the wavelength and time-dependent modifications of the object material dielectric function. Its application is illustrated in the case of single silver nanospheres and gold nanorods, as well as on ensembles of noble metal nanoparticles and metal-semiconductor nano-hybrids. This quantitative analysis also permits to elucidate the physical mechanisms at the origin of ultrafast nonlinearities in confined metals at different timescales.
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. This behavior can be reproduced assuming the LSPR width linearly depends on the inverse of an effective length proportional to the square root of the particle surface with the same slope as that recently determined for silica-coated silver nanospheres.
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