0000000000200126
AUTHOR
Alain Mermet
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.
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…
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…
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…
Inelastic neutron scattering due to acoustic vibrations confined in nanoparticles: theory and experiment
The inelastic scattering of neutrons by nanoparticles due to acoustic vibrational modes (energy below 10 meV) confined in nanoparticles is calculated using the Zemach-Glauber formalism. Such vibrational modes are commonly observed by light scattering techniques (Brillouin or low-frequency Raman scattering). We also report high resolution inelastic neutron scattering measurements for anatase TiO2 nanoparticles in a loose powder. Factors enabling the observation of such vibrations are discussed. These include a narrow nanoparticle size distribution which minimizes inhomogeneous broadening of the spectrum and the presence of hydrogen atoms oscillating with the nanoparticle surfaces which enhan…
Simple model for the vibrations of embedded elastically cubic nanocrystals
The purpose of this work is to calculate the vibrational modes of an elastically anisotropic sphere embedded in an isotropic matrix. This has important application to understanding the spectra of low-frequency Raman scattering from nanoparticles embedded in a glass matrix. First some low frequency vibrational modes of a free cubically elastic sphere are found to be nearly independent of one combination of elastic constants. This is then exploited to obtain an isotropic approximation for these modes which enables to take into account the surrounding isotropic matrix. This method is then used to quantatively explain recent spectra of gold and copper nanocrystals in glasses.
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 ...
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 …