An investigation of the vibrational density of states (VDOS) in silver nanocrystals is performed using Raman scattering. A specific sample architecture, setup configuration, and original elaboration process are used in order to take simultaneously advantage of spectrally and spatially localized surface plasmon resonance, optical amplification, and dark-field spectroscopy. Disentangling the contributions of atom vibrations and electron-hole excitations (i.e., the so-called "background" in surface-enhanced Raman scattering) is performed. The extracted VDOS is successfully compared with theoretical ones obtained by atomic scale simulations. The effects of size, strain, and disorder on the VDOS are analyzed; in particular, the strain effect is investigated experimentally using the geometrical phase analysis coupled with high-resolution transmission electron microscopy. This work offers an opportunity to examine thermodynamic properties, like specific heat, at the nanoscale.
A strategy to design and fabricate hybrid metallic-dielectric substrates for optical spectroscopy and imaging is proposed. Different architectures consisting of three-dimensional patterns of metallic nanoparticles embedded in dielectric layers are conceived to simultaneously exploit the optical interference phenomenon in stratified media and localized surface plasmon resonances on metal nanoparticles. These structures are based on a simultaneous control of opto-electronic properties at three scales (3S) (~2/20/200 nm) and along three directions (3D). By ultralow energy ion implantation through a microfabricated stencil we precisely control the size, density, and location of silver nanoparticles embedded in silica/silicon thin films. Elastic (Rayleigh) and inelastic (Raman) scattering imaging assisted by simulations were used to analyze the optical response of these "3S-3D" patterned layers. The reflectance contrast is strongly enhanced when resonance conditions between the stationary electromagnetic field in the dielectric matrix and the localized plasmon resonance in the silver nanoparticles are realized. The potential of these 3S-3D metal-dielectric structures as surface-enhanced Raman scattering substrates is demonstrated. These novel kinds of plasmonic-photonic architectures are reproducible and stable; they preserve flat and chemically uniform surfaces, offering opportunities for the development of efficient and reusable substrates for optical spectroscopy and imaging enhancement.
Since the discovery of surface-enhanced Raman scattering (SERS) 40 years ago, the origin of the "background" that is systematically observed in SERS spectra has remained questionable. To deeply analyze this phenomenon, plasmon-resonant Raman scattering was recorded under specific experimental conditions on a panel of composite multilayer samples containing noble metal (Ag and Au) nanoparticles. Stokes, anti-Stokes, and wide, including very low, frequency ranges have been explored. The effects of temperature, size (in the nm range), embedding medium (SiO 2 , Si 3 N 4 , or TiO 2 ) or ligands have been successively analyzed. Both lattice (Lamb modes and bulk phonons) and electron (plasmon mode and electron-hole excitations) dynamics have been investigated. This work confirms that in Ag-based nanoplasmonics composite layers, only Raman scattering by single-particle electronic excitations accounts for the background. This latter appears as an intrinsic phenomenon independently of the presence of molecules on the metallic surface. Its spectral shape is well described by revisiting a model developed in the 1990s for analyzing electron scattering in dirty metals, and used later in superconductors. The g s factor, that determines the effective mean-free path of free carriers, is evaluated, g expt s = 0.33 ± 0.04, in good agreement with a recent evaluation based on time-dependent local density approximation g theor s = 0.32. Confinement and interface roughness effects at the nanometer range thus appear crucial to understand and control SERS enhancement and more generally plasmon-enhanced processes on metallic surfaces.
Fe-Au core-shell nanoparticles displaying an original polyhedral morphology have been successfully synthesized through a physical route. Analyses using transmission electron microscopy show that the Au shell forms truncated pyramids epitaxially grown on the (100) facets of the iron cubic core. The evolution of the elastic energy and strain field in the nanoparticles as a function of their geometry and composition is calculated using the finite-element method. The stability of the remarkable centered core-shell morphology experimentally observed is attributed to the weak elastic energy resulting from the low misfit at the Fe/Au (100) interface compared to the surface energy contribution.
Surface enhanced Raman scattering (SERS) is generally and widely used to enhance the vibrational fingerprint of molecules located at the vicinity of noble metal nanoparticles. In this work, SERS is originally used to enhance the own vibrational density of states (VDOS) of nude and isolated gold nanoparticles. This offers the opportunity of analyzing finite size effects on the lattice dynamics which remains unattainable with conventional techniques based on neutron or x-ray inelastic scattering. By reducing the size down to few nanometers, the role of surface atoms versus volume atoms become dominant, and the “text-book” 3D-2D transition on the dynamical behavior is experimentally emphasized. “Anomalies” that have been predicted by a large panel of simulations at the atomic scale, are really observed, like the enhancement of the VDOS at low frequencies or the occurrence of localized modes at frequencies beyond the cut-off in bulk. Consequences on the thermodynamic properties at the nanoscale, like the reduction of the Debye temperature or the excess of the specific heat, have been evaluated. Finally the high sensitivity of reminiscent bulk-like phonons on the arrangements at the atomic scale is used to access the morphology and internal disorder of the nanoparticles.
Fe-Au core-shell nanoparticles embedded in an amorphous alumina matrix are synthesized at high temperature using magnetron sputtering. The nanoparticles display a single-crystal Fe core covered by a crystalline Au shell epitaxially grown on the different core facets. The morphology of the grown nanoparticles is analyzed by transmission electron microscopy, while their structural details are resolved at the atomic scale using probecorrected high-angle annular dark-field scanning transmission microscopy. Two different epitaxial relationships at the Au/Fe interface are observed at low Au coverage, whereas only one type of interface orientation remains when the shell thickness exceeds 3 monolayers (MLs). This leads to a drastic Fe core transformation from a Wulff shaped crystal towards a nanocube. This core transformation drives a surface reconstruction resulting in a combination of open and close-packed strain free facets, offering different opportunities for molecule binding. In addition, our experiments show that the magnetic properties of the Fe core are preserved by the Au shell and that the 10 nm size of the grown nanoparticles favors a superparamagnetic behavior, suitable for biomedical applications.
Ultra low energy ion implantation is a promising technique for the wafer-scale fabrication of Silver nanoparticle planar arrays embedded in thermal silica on silicon substrate. The stability versus time of these nanoparticles is studied at ambient conditions on a time scale of months. The plasmonic signature of Ag NPs vanishes several months after implantation for as-implanted samples, while samples annealed at intermediate temperature under N2 remain stable. XPS and HREM analysis evidence the presence of Silver oxide nanoparticles on aged samples and pure Silver nanoparticles on the annealed ones. This thermal treatment does not modify the size-distribution or position of the particles but is very efficient in stabilizing the metallic particles and to prevent any form of oxidation.
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