Continuum elastic sphere vibrations as a model for low-lying optical modes in icosahedral quasicrystals

The nearly dispersionless, so-called "optical" vibrational modes observed by inelastic neutron scattering from icosahedral Al-Pd-Mn and Zn-Mg-Y quasicrystals are found to correspond well to modes of a continuum elastic sphere that has the same diameter as the corresponding icosahedral basic units of the quasicrystal. When the sphere is considered as free, most of the experimentally found modes can be accounted for, in both systems. Taking into account the mechanical connection between the clusters and the remainder of the quasicrystal allows a complete assignment of all optical modes in the case of Al-Pd-Mn. This approach provides support to the relevance of clusters in the vibrational prop…

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…

Boson peak and hybridization of acoustic modes with vibrations of nanometric heterogeneities in glasses

9 pages; International audience; The low-frequency dynamics in glasses is compared with that in icosahedral quasicrystals. For both arrangements of matter, the existence of nanometric heterogeneities, implying the existence of a nanometric inhomogeneous elastic network, is expected to play a crucial role. Thanks to this comparison, mostly based on inelastic x-ray (neutron) scattering data, it is proposed that the excess of vibrational density of states observed in both materials is due to the hybridization of longitudinal and transverse acoustic modes with modes localized around the heterogeneities.

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

Millimeter wave absorption by confined acoustic modes in CdSe/CdTe core-shell quantum dots

International audience; Taking advantage of the specific core-shell charge separation structure in the CdSe/CdTe core-shell Type-II quantum dots (QDs), we experimentally observed the resonant-enhanced dipolar interaction between millimeter-wave (MMW) photons and their corresponding (l = 1) confined acoustic phonons. With proper choice of size, the absorption band can be tuned to desired frequency of MMW imaging. Exploiting this characteristic absorption, in a fiber-scanned MMW imaging system, we demonstrated the feasibility of CdSe/CdTe QDs as the contrast agents of MMW imaging.

A multi-step mechanism and integrity of titanate nanoribbons.

A one-step hydrothermal treatment of TiO2 powders under strongly basic conditions has been used to synthesize titanate nanoribbons. The nanoparticles were thoroughly characterized using several methods including transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectrometry (XPS) to determine their morphological, structural and chemical characteristics. The influence of the nature and size of the TiO2 precursor and of the reaction duration on the formation of the nanoribbons was investigated. The conditions required to obtain only titanate nanoribbons with a width ranging from 100 to 200 nm and several tens of micrometers in length w…

Acoustic Vibrations in Nanoparticles

High precision numerical estimates of acoustic phonon frequencies of nonspherical nanoparticles

We introduce an adapted method for calculating the acoustic vibrational frequencies of arbitrarily shaped nanoparticles to high precision. Molecular dynamics simulation results are tested against exact solutions for a free sphere, a hollow sphere and a spheroid. This permits theoretical predictions of the frequencies of peaks in low frequency Raman spectra. Our results demonstrate that vibrational frequencies can be calculated for a wide range of low frequency modes with accuracies on the order of a tenth of a percent.

Acousto-Plasmonic Hot Spots: Driving Enhanced Raman Scattering in Metallic Nanoparticles

We study theoretically and experimentally the coupling of acoustic vibrations (phonons) and surface plasmons in metallic nano-objects. The modulation of the surface charge density allows for the interpretation of experimental Raman-Brillouin spectra in silver nanorods.

Growth of glass-embedded Cu nanoparticles: A low-frequency Raman scattering study

International audience; Several populations of Cu spherical nanoparticles grown in a silicate glass at different temperatures with respect to the glass transition temperature were studied using high-resolution, low-frequency Raman scattering and optical absorption. The analysis of the spectra shows that the annealing of the doped glass at temperatures close to T-g leads to the formation of metallic copper nanoparticles with high crystallinity, whereas lower-temperature and higher-temperature annealings result in the formation of poorer nanoparticle assemblies in terms of size distribution and/or nanocrystallinity. It is also shown that in the case where the optical data do not unambiguously…

Acoustic vibrations of metal nanoparticles: high order radial mode detection

The vibrational radial modes of silver nanospheres embedded in a glass matrix are investigated using a high sensitivity femtosecond pump-probe technique. The results yield evidence for coherent launching of the fundamental and higher order radial modes in agreement with a sphere dilation mediated excitation model. The results are consistent with low-frequency Raman scattering experiments.

Experimental investigation of the grain size dependence of the hydrolysis of LiH powder

International audience; The hydrolysis reaction of LiH powder has been investigated in order to determine the products, rates and mechanisms of this reaction and the influence of the experimental parameters. Raman spectroscopy, X-ray diffraction and gravimetric analysis were used. It was shown that the product of hydrolysis was the hydroxide of lithium (LiOH) for low partial pressure of water (≈50 Pa) and LiOH*H2O for a higher partial pressure of water (>2000 Pa). Moreover, data obtained using gravimetric analysis inside a glove box containing a controlled partial pressure of water (500 ppmv/50 Pa at 25 °C) were used to determine the rate of the reaction versus particle size. The experiment…

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…

Bridgman growth of paratellurite single crystals

Abstract The growth of paratellurite single crystals by the vertical-gradient freezing technique is reported for the first time. Boules of 120 mm long and 25 mm in diameter were obtained under a temperature gradient of 10°C cm −1 and translation rates lower than 0.6 mm h −1 . The spatial distribution of defects along the growth axis reveals a continuous evolution of the free convective fluid-flow regime as growth proceeds. Gas bubbles and dark inclusions rejected to the periphery in the upper part of the crystal are observed to lay preferentially in (1 0 0), (0 0 1), ( 1 1 ¯ 0 ) and (1 1 2) crystallographic planes. Among them, SEM and microprobe analyses evidenced the presence of metallic p…

Acoustic vibrations of nano-objects

Acoustic vibrations of nanoparticles were first observed using inelastic light scattering 4 decades ago. Significant advances in the synthesis of nano-objects and frequency and time-domain spectroscopy techniques have made it possible to investigate the sensitivity of these vibrations to the structure (size, shape, crystal structure) and environment of the nano-objects. This lecture will present an overview of this field and focus in particular on recent experimental results and models required to describe the acoustic vibrations of various kinds of nano-objects and their symmetry.References:- E. Duval, A. Boukenter, and B. Champagnon, Phys. Rev. Lett. 56, 2052 (1986)- H. Portalès, N. Goube…

Temperature rise during laser-induced self-organization of nanoparticle gratings revealed by Raman microspectroscopy and electron microscopy

International audience

Efficient photo-thermal activation of gold nanoparticle-doped polymer plasmonic switches

International audience; We report on the photo-thermal activation of dielectric loaded plasmonic switches comprised of gold nanoparticle-doped polymer deposited onto a gold film. The plasmonic switches rely on a multi-mode interferometer design and are fabricated by electron beam lithography applied to a positive resin doped with gold nanoparticles at a volume ratio of 0.52%. A cross-bar switching is obtained at telecom wavelengths by pumping the devices with a visible beam having a frequency within the localized surface plasmon resonance band of the embedded nanoparticles. By comparing the switching performances of doped and undoped devices, we show that for the modest doping level we cons…

Effect of physical aging on the low-frequency vibrational density of states of a glassy polymer

The effects of the physical aging on the vibrational density of states (VDOS) of a polymeric glass is studied. The VDOS of a poly(methyl methacrylate) glass at low-energy (<15 meV), was determined from inelastic neutron scattering at low-temperature for two different physical thermodynamical states. One sample was annealed during a long time at temperature lower than Tg, and another was quenched from a temperature higher than Tg. It was found that the VDOS around the boson peak, relatively to the one at higher energy, decreases with the annealing at lower temperature than Tg, i.e., with the physical aging.

Increased heating of metallic nanoparticles for lower deposited light energy: measurement and explanation of a counter-intuitive behavior

International audience

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.

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.

Growth and size distribution of Au nanoparticles in annealed Au/TiO2 thin films

Abstract Nanocomposites consisting of noble metal nanoparticles (NPs) embedded in TiO2 thin films are of great interest for applications in optoelectronics, photocatalysis and solar-cells for which the plasmonic properties of the metal NPs play a major role. This work investigates the first stages of the formation of gold NPs by thermal annealing of Au-doped TiO2 thin films grown by magnetron sputtering. A low concentration of gold in the films is considered (5 at.%) in order to study the first stages of the formation of the NPs. Raman spectroscopy is used to follow the crystallization of TiO2 when increasing the annealing temperature. In addition, low-frequency Raman scattering (LFRS) is u…

Raman characterization of Pb2Na1−xLaxNb5−xFexO15 and Pb0.5(5−x)LaxNb5−xFexO15 (0≤x≤1) solid solutions

Abstract The ferroelectric compounds Pb 2 Na 1− x La x Nb 5− x Fe x O 15 and Pb 0.5(5− x ) La x Nb 5− x Fe x O 15 (0≤ x ≤1) with the tungsten bronze type structure have been investigated using Raman spectroscopy. The evolution of the spectra as a function of composition at room temperature is reported. In the frequency range 200–1000 cm −1 three main A 1 phonons around 240 ( υ 1 ), 630 ( υ 2 ) and 816 ( υ 3 ) cm −1 were observed. The broadening of the Raman lines for high values of x originates from a significant structural disorder. This is in good agreement with the relaxor character of these compositions. The lowest-frequency part of the spectra, below 180 cm −1 , reveals a structural ch…

Atomic Layer Deposition of Au-TiO2 inverse opals for the visible light photocatalysis of dyesdegradation

The pollution of waste water due to organic dyes used in the textile and chemical industries is an important environmental issue. Inverse opals (IO) offer a great potential for increasing the efficiency of their degradation by semiconductor photocatalysts such as TiO2 by the synergy of high specific surface and photonic crystal properties [1]. Doping TiO2 with gold nanoparticles is another possible strategy to enhance its photocatalytic activity by increasing its optical absorption in the visible range [2].This work reports the synthesis of Au-TiO 2 IO films by Atomic Layer Deposition and the study of their visible-light photocatalytic activity for the degradation of methylene blue in water…

Functionalized Fe3O4 nanoparticles: influence of ligand addition sequence and pH during their continuous hydrothermal synthesis

In this study we report various new efficient ways to synthesize and modify in situ magnetite (Fe3O4) iron oxide nanoparticles (NPs). Thanks to an apparatus especially developed for this new method of grafting, the NPs have been synthesized and functionalized by 3,4-dihydroxyhydrocinnamic acid (DHCA) or 3,4-dihydroxy-L-phenylalanine (LDOPA) in one step and under hydrothermal conditions using varying concentration ratios ([organic molecules]/[ferrous and ferric ions]). The organic molecules were added before or after the NP synthesis. The addition of these organic molecules modifies the structure, the morphology, the oxidation degree and the growth of the crystallites. Adding the organic mol…

Thermal effects on the growth by metal organic chemical vapour deposition of TiO2 thin films on (100) GaAs substrates

Abstract TiO 2 thin films were deposited on (100) GaAs substrates by LP-MOCVD with deposition temperatures ( T d ) ranking from 450 to 750 °C. The structure of these layers was studied by X-ray diffraction (XRD) and Raman spectroscopy. The growth of the TiO 2 anatase phase was observed for T d T d >600 °C. Finally, X-ray photoelectron spectrometry (XPS) and secondary ion mass spectroscopy (SIMS) experiments showed the presence of small quantities of Ga and As through the whole film thickness, slightly increasing at the surface of the layers. This result was related to the SEM observations and explained by considering the growth conditions.

Damping by bulk and shear viscosity for confined acoustic phonons of a spherical virus in water

International audience; A sphere-like virus in water is modeled as a homogeneous isotropic elastic continuum sphere in contact with an infinite viscous compressible Newtonian fluid. The frequencies and damping of the confined vibrational modes of the sphere are calculated for the material parameters of a virus in water. While the effects of viscosity are found to be negligible for a virus-like sphere of macroscopic size, for nanoscale viruses both the frequency and damping of the vibrational modes are significantly affected by the viscosity of the water. Furthermore, both shear viscosity and bulk viscosity play an important role.

From crystal to glass-like thermal conductivity in crystalline minerals

Équipe 103 : Composés intermétalliques et matériaux hybrides; International audience; The ability of some materials with a perfectly ordered crystal structure to mimic the heat conduction of amorphous solids is a remarkable physical property that finds applications in numerous areas of materials science, for example, in the search for more efficient thermoelectric materials that enable to directly convert heat into electricity. Here, we unveil the mechanism in which glass-like thermal conductivity emerges in tetrahedrites, a family of natural minerals extensively studied in geology and, more recently, in thermoelectricity. By investigating the lattice dynamics of two tetrahedrites of very c…