Sorting of Enhanced Reference Raman Spectra of a Single Amino Acid Molecule

In this contribution, we report the identification of the principal reference Raman spectra of a single cystein molecule. To that purpose, we design an active Surface Enhanced Raman Spectroscopy (SERS) template based on surfactant-less Chebyshev nanoparticles operating in a microfluidic platform. A principal component analysis is obtained from fluctuating spectra to sort the reference spectra of cystein. The assignment of Raman bands brings new insight into the conformation of an amino acid adsorbed onto gold nanoparticle.

Mechanical Coupling in Gold Nanoparticles Supermolecules Revealed by Plasmon-Enhanced Ultralow Frequency Raman Spectroscopy

International audience; Acoustic vibrations of assemblies of gold nanoparticles were investigated using ultralow frequency micro-Raman scattering and finite element simulations. When exciting the assemblies resonantly with the surface plasmon resonance of electromagnetically coupled nano-particles, Raman spectra present an ultralow frequency band whose frequency lies below the lowest Raman active Lamb mode of single nanoparticles that was observed. This feature was ascribed to a Raman vibration mode of gold nanoparticle " supermolecules " , that is, nanoparticles mechanically coupled by surrounding polymer molecules. Its measured frequency is inversely proportional to the nanoparticle diame…

Enlightening the acoustic vibrations of single crystalline gold nanorods by very low-frequency Raman scattering

Contact laws between nanoparticles: the elasticity of a nanopowder

International audience; Studies of the mechanical contact between nanometer-scale particles provide fundamental insights into the mechanical properties of materials and the validity of contact laws at the nanoscale which are still under debate for contact surfaces approaching atomic dimensions. Using in situ Brillouin light scattering under high pressure, we show that effective medium theories successfully predict the macroscopic sound velocities in nanopowders if one takes into account the cementation of the contacts Our measurements suggest the relevance of the continuum approach and effective medium theories to describe the contact between nanoparticles of diameters as small as 4 nm, i.e…

Surface plasmons and vibrations of self-assembled silver nanocolumns

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Inelastic Light Scattering Contribution to the Study of the Onset of Sintering of a Nanopowder

International audience; The onset of the sintering of 5 nm ZrO2 and TiO2 nanoparticles is investigated by various methods including inelastic light scattering. A special attention is paid to low-frequency Raman spectra where scattering from confined acoustic vibrations and quasielastic scattering manifest. Significant changes are observed between samples sintered at different temperatures or applied forces. A detailed analysis of the spectra enables to follow the variation of the size of the nanoparticles, the surface area, and the formation of internanoparticles necks in the sintered materials. Finally, low-frequency scattering is shown to be more sensitive to the onset of sintering than m…

The mass load effect on the resonant acoustic frequencies of colloidal semiconductor nanoplatelets

Resonant acoustic modes of ultrathin CdS and CdSe colloidal nanoplatelets (NPLs) with varying thicknesses were probed using low frequency Raman scattering. The spectra are dominated by an intense band ascribed to the thickness breathing mode of the 2D nanostructures. The measured Raman frequencies show strong deviations with respect to the values expected for simple bare plates, all the more so as the thickness is reduced. The deviation is shown to arise from the additional mass of the organic ligands that are bound to the free surfaces of the nanoplatelets. The calculated eigen frequencies of vibrating platelets weighed down by the mass of the organic ligands are in very good agreement wit…

Influence of the Number of Nanoparticles on the Enhancement Properties of Surface-Enhanced Raman Scattering Active Area: Sensitivity versus Repeatability

In the present work, the combination of chemical immobilization with electron beam lithography enables the production of sensitive and reproducible SERS-active areas composed of stochastic arrangements of gold nanoparticles. The number of nanoparticles was varied from 2 to 500. Thereby a systematic analysis of these SERS-active areas allows us to study SERS efficiency as a function of the number of nanoparticles. We found that the experimental parameters are critical, in particular the size of the SERS-active area must be comparable to the effective area of excitation to obtained reproducible SERS measurements. The sensitivity has also been studied by deducing the number of NPs that generat…

Surface enhanced Raman scattering of silver sensitized cobalt nanoparticles in metal–dielectric nanocomposites

We report the preparation of a new type of nanocomposite containing cobalt and silver nanoparticles organized in parallel layers with a well controlled separation. This arrangement allows the observation of an enhanced low-frequency Raman signal at the vibration frequency of cobalt nanoparticles excited through the surface plasmons of silver nanoparticles. Numerical simulations of the electric field confirm the emergence of hot spots when the separation between silver and cobalt nanoparticles is small enough. © IOP Publishing Ltd.

Acousto-plasmonic coupling in engineered metal nanocomposites

This work shows the production of self-assembled elongated nano-objects embedded in an oxide host oriented perpendicular to the substrate and their acousto-plasmonic dynamics. Electromagnetic “hot spots” are created that activate anomalous Raman vibrational modes.

Inelastic light scattering by the vibrational modes of single gold nanocrystals

The measurement of acoustic vibrational modes is fundamental to the full comprehension of the mechanical properties of nano-objects, since they are related to the intrinsic characteristics of the material, such as crystallinity, size, shape, and elasticity. Furthermore, it has been shown that modifications in local environment can induce the appearance of new features in the inelastic light scattering spectra of nanoparticles that do not follow the usual selection rules. In this sense, optical spectroscopy techniques represent a powerful tool to study the vibrational modes of nano-objects and address both their intrinsic properties and their interaction with light, which plays a key role fo…

Optical and Acoustic Vibrations Confined in Anatase TiO2 Nanoparticles under High-Pressure

International audience; The effect of an applied high pressure on the optical and acoustic vibrations of small anatase TiO2 nanoparticles is studied using Raman scattering. All the Raman peaks show a significant variation of their frequency with pressure, except for the low-frequency peak which is due to acoustic vibrations confined in the nanoparticles. These variations (or lack thereof) are compared to first-principles calculations of the stiffness tensor and phonons of bulk anatase TiO2 as a function of pressure. In particular, the variation of the shape of the low-frequency peak is explained by the increase of the elastic anisotropy of anatase TiO2 as pressure is increased.

Quasi-free nanoparticle vibrations in a highly-compressed ZrO2 nanopowder

Several-nanometer-size mechanical oscillators, or nanoresonators, may complement electronic and optical technologies in future terahertz devices, but they can be useful only if they can be made to ...

Tuning of an Optical Dimer Nanoantenna by Electrically Controlling Its Load Impedance

International audience; Optical antennas are elementary units used to direct optical radiation to the nanoscale. Here we demonstrate an active control over individual antenna performances by an external electrical trigger. We find that by an in-plane command of an anisotropic load medium, the electromagnetic interaction between individual elements constituting an optical antenna can be controlled, resulting in a strong polarization and tuning response. An active command of the antenna is a prerequisite for directing light wave through the utilization of such a device.

Environmental effects on the natural vibrations of nanoplatelets: a high pressure study.

International audience; Resonant acoustic modes from ultrathin CdS colloidal nanoplatelets (NPLs) are probed under high pressure using low frequency Raman spectroscopy. In particular we focus on the characterization of the recently evidenced mass load effect that is responsible for a significant downshift of the NPL breathing frequency due to the inert mass of organic ligands. We show that a key parameter in the observation of the mass effect is whether the surrounding medium is able to support THz acoustic wave propagation, at a frequency close to that of the inorganic vibrating core. At low pressures, surface organic molecules show a single particle-like behavior and a strong mass effect …

Discerning the Origins of the Amplitude Fluctuations in Dynamic Raman Nanospectroscopy

International audience; We introduce a novel experimental and analytical method for discerning rare surface-enhanced Raman scattering (SERS) events observable at the nanoscale. We show that the kinetics of the Raman activity recorded on an isolated nanostructure is punctuated by intense and rare events of large amplitude and spectral variations. The fluctuations of thousands of SERS spectra were analyzed statistically in terms of power density functions, and the occurrence of the rare events was quantified by a wavenumber statistics. Our analysis enables one to extract valuable and unique spectroscopic signature of Raman variations usually hidden in time-average or space-average measurement…