Pierre-Eugène Coulon

Rayleigh-like instability in the ion-shaping of Au–Ag alloy nanoparticles embedded within a silica matrix

We have studied how spherical 23 ± 3 nm Au(45)Ag(55) nanoparticles embedded within a silica matrix transform into prolate nanorods and nanowires by irradiating them with swift heavy ions. Samples were irradiated at room temperature and normal incidence with 74 MeV Kr and 36 MeV S ions for fluences up to 1.0 × 10(15) cm(-2). We demonstrate the existence of two regimes: (i) below a critical fluence, ∼ 2.0 × 10(14) cm(-2), the transformation of the spherical nanoparticle into a nanorod is an individual process, i.e. each nanoparticle transforms into a single nanorod; (ii) for larger fluences the transformation from nanorod to nanowire becomes a collective process, i.e. the break up and dissolution of unstable nanorods contribute to the growth of long nanowires. The passage from the first to the second regime can be interpreted in terms of a Rayleigh-like instability under irradiation. The latter becomes active when the diameter of the nanowire approaches its saturation width under irradiation. Furthermore, we show that the composition of the alloy is only slightly modified during the ion-shaping process. Finally, the energy and the fluence thresholds for deformation and the deformation strain-rate are estimated.

Fabrication of Ion-Shaped Anisotropic Nanoparticles and their Orientational Imaging by Second-Harmonic Generation Microscopy.

Ion beam shaping is a novel and powerful tool to engineer nanocomposites with effective three-dimensional (3D) architectures. In particular, this technique offers the possibility to precisely control the size, shape and 3D orientation of metallic nanoparticles at the nanometer scale while keeping the particle volume constant. Here, we use swift heavy ions of xenon for irradiation in order to successfully fabricate nanocomposites consisting of anisotropic gold nanoparticle that are oriented in 3D and embedded in silica matrix. Furthermore, we investigate individual nanorods using a nonlinear optical microscope based on second-harmonic generation (SHG). A tightly focused linearly or radially-polarized laser beam is used to excite nanorods with different orientations. We demonstrate high sensitivity of the SHG response for these polarizations to the orientation of the nanorods. The SHG measurements are in excellent agreement with the results of numerical modeling based on the boundary element method.

Strain engineering of photo-induced phase transformations in Prussian blue analogue heterostructures

Heterostructures based on Prussian blue analogues (PBA) combining photo- and magneto-striction have shown a large potential for the development of light-induced magnetization switching. However, studies of the microscopic parameters that control the transfer of the mechanical stresses across the interface and their propagation in the magnetic material are still too scarce to efficiently improve the elastic coupling. Here, this coupling strength is tentatively controlled by strain engineering in heteroepitaxial PBA core-shell heterostructures involving the same Rb0.5Co[Fe(CN)6]0.8·zH2O photostrictive core and isostructural shells of similar thickness and variable mismatch with the core lattice. The shell deformation and the optical electron transfer at the origin of photostriction are monitored by combined in situ and real time synchrotron X-ray powder diffraction and X-ray absorption spectroscopy under visible light irradiation. These experiments show that rather large strains, up to +0.9%, are developed within the shell in response to the tensile stresses associated with the expansion of the core lattice upon illumination. The shell behavior is, however, complex, with contributions in dilatation, in compression or unchanged. We show that a tailored photo-response in terms of strain amplitude and kinetics with potential applications for a magnetic manipulation using light requires a trade-off between the quality of the interface (which needs a small lattice mismatch i.e. a small a-cubic parameter for the shell) and the shell rigidity (decreased for a large a-parameter). A shell with a high compressibility that is further increased by the presence of misfit dislocations will show a decrease in its mechanical retroaction on the photo-switching properties of the core particles.

Ion-shaping of embedded gold hollow nanoshells into vertically aligned prolate morphologies

Ion beam shaping is a novel technique with which one can shape nano-structures that are embedded in a matrix, while simultaneously imposing their orientation in space. In this work, we demonstrate that the ion-shaping technique can be implemented successfully to engineer the morphology of hollow metallic spherical particles embedded within a silica matrix. The outer diameter of these particles ranges between 20 and 60 nm and their shell thickness between 3 and 14 nm. Samples have been irradiated with 74 MeV Kr ions at room temperature and for increasing fluences up to 3.8 × 1014 cm−2. In parallel, the experimental results have been theoretically simulated by using a three-dimensional code based on the thermal-spike model. These calculations show that the particles undergo a partial melting during the ion impact, and that the amount of molten phase is maximal when the impact is off-center, hitting only one hemisphere of the hollow nano-particle. We suggest a deformation scenario which differs from the one that is generally proposed for solid nano-particles. Finally, these functional materials can be seen as building blocks for the fabrication of nanodevices with really three-dimensional architecture.

Stable HfO2 based Layers Fabricated by RF Magnetron Sputtering

Structural and composition properties of HfO2-based layers fabricated by RF magnetron sputtering were studied by means of X-ray diffraction and transmission electron microscopy, Energy dispersive spectroscopy and ATR-FTIR techniques versus the deposition parameters and post-deposition annealing treatment. It was observed that the temperature at which amorphous-crystalline transformation of pure HfO2 layers occurs depends on deposition conditions. It was found that silicon incorporation in HfO2 matrix plays main role in the stability of the layers and allows to increase the temperature of layer crystallization up to 900-1100 °C.