G. BenAssayag

End of range defects in Ge

We show that the solid-phase epitaxial regrowth of amorphous layers created by ion implantation in Ge results in the formation of extended defects of interstitial-type. During annealing, these defects evolve in size and density following, as in Si, an Ostwald ripening mechanism. However, this process becomes nonconservative as the annealing temperature increases to 600u2009°C. This suggests that the recombination/annihilation of Ge interstitial atoms becomes important at these temperatures. These results have important implications for the modeling of diffusion of implanted dopants in Ge.

The synthesis of single layers of Ag nanocrystals by ultra-low-energy ion implantation for large-scale plasmonic structures

Single layers of silver (Ag) nanoparticles embedded in silica (SiO2) have been fabricated by ultra-low-energy ion implantation. The distance between the Ag particles and the free SiO2 surface is controlled with nanometer precision. Raman scattering and reflectivity measurements strongly correlate to transmission electron microscopy analyses, allowing the use of these non-invasive techniques to monitor structural and dynamical properties. These results open up new opportunities to manipulate electromagnetic near-field interactions on wafer-scale plasmonic devices.

Scaling size of the interplay between quantum confinement and surface related effects in nanostructured silicon

Si nanocrystals (NCs) embedded in a SiO2 matrix provide an exemplar curved nanostructured interface to evidence the competition between surface states and quantum confinement (QC) effects. The study of the energy band alignment as a function of NCs size (<5u2009nm) clarifies their interplay and identifies, with subnanometric resolution, three different regimes. Primarily QC affects the conduction band, then surface effects pin the conduction states, and finally QC starts to modify the valence band. A way to study how different nanoscale configurations compete with pure quantum properties is established.

Stability of Ag nanocrystals synthesized by ultra-low energy ion implantation in SiO2 matrices

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.

In-plane organization of silicon nanocrystals embedded in SiO2 thin films

Nanofabrication of buried structures with dimensions below 5xa0nm and with controlled 3D-positioning at the nanoscale was attempted to open new routes to future nanodevices where single nanostructures could be systematically interfaced. A typical example is ultralow-energy ion beam synthesis where already the depth positioning of embedded arrays of silicon nanocrystals can be finely controlled with nanometric precision. In this study, we investigated for the first time the control of the in-plane organization of the nanocrystals using a legitimate patterning option for microelectronic industries, self-assembled block-copolymer. The compatibility with the ultralow-energy ion beam synthesis process of polymeric nanoporous films used as mask was demonstrated together with the capability to control in 3D the organization of Si nanocrystals. The resulting nano-organization consists in a hexagonal array of 20xa0nm wide nanovolumes containing on average 8 nanocrystals embedded at a controlled depth within a silica matrix.

Assessing bio-available silver released from silver nanoparticles embedded in silica layers using the green algae Chlamydomonas reinhardtii as bio-sensors

Silver nanoparticles (AgNPs) because of their strong antibacterial activity are widely used in health-care sector and industrial applications. Their huge surface-volume ratio enhances the silver release compared to the bulk material, leading to an increased toxicity for microorganisms sensitive to this element. This work presents an assessment of the toxic effect on algal photosynthesis due to small (size <20nm) AgNPs embedded in silica layers. Two physical approaches were originally used to elaborate the nanocomposite structures: (i) low energy ion beam synthesis and (ii) combined silver sputtering and plasma polymerization. These techniques allow elaboration of a single layer of AgNPs embedded in silica films at defined nanometer distances (from 0 to 7nm) beneath the free surface. The structural and optical properties of the nanostructures were studied by transmission electron microscopy and optical reflectance. The silver release from the nanostructures after 20h of immersion in buffered water was measured by inductively coupled plasma mass spectrometry and ranges between 0.02 and 0.49μM. The short-term toxicity of Ag to photosynthesis of Chlamydomonas reinhardtii was assessed by fluorometry. The obtained results show that embedding AgNPs reduces the interactions with the buffered water free media, protecting the AgNPs from fast oxidation. The release of bio-available silver (impacting on the algal photosynthesis) is controlled by the depth at which AgNPs are located for a given host matrix. This provides a procedure to tailor the toxicity of nanocomposites containing AgNPs.

Acoustics at nanoscale: Raman–Brillouin scattering from thin silicon-on-insulator layers

We report on Raman–Brillouin scattering from thin single silicon layers. Starting from a 33 nm silicon-on-insulator structure, a series of layers with progressively decreasing thicknesses was prepared using a chemical treatment consisting of oxide stripping/formation cycles. In order to determine these thicknesses, experimental Raman–Brillouin spectra are compared to calculations performed in the frame of the photoelastic model. We demonstrate that subnanometer changes in the silicon layer thickness can be derived from a proper analysis of the spectral response. It is shown that a 1 nm thick oxide forms during the chemical treatment.

Ag doped silicon nitride nanocomposites for embedded plasmonics

The localized surface plasmon-polariton resonance (LSPR) of noble metal nanoparticles (NPs) is widely exploited for enhanced optical spectroscopies of molecules, nonlinear optics, photothermal therapy, photovoltaics, or more recently in plasmoelectronics and photocatalysis. The LSPR frequency depends not only of the noble metal NP material, shape, and size but also of its environment, i.e., of the embedding matrix. In this paper, Ag-NPs have been fabricated by low energy ion beam synthesis in silicon nitride (SiNx) matrices. By coupling the high refractive index of SiNx to the relevant choice of dielectric thickness in a SiNx/Si bilayer for an optimum antireflective effect, a very sharp plasmonic optical interference is obtained in mid-range of the visible spectrum (2.6u2009eV). The diffusion barrier property of the host SiNx matrix allows for the introduction of a high amount of Ag and the formation of a high density of Ag-NPs that nucleate during the implantation process. Under specific implantation conditions, in-plane self-organization effects are obtained in this matrix that could be the result of a metastable coarsening regime.

Extraction of the characteristics of Si nanocrystals by the charge pumping technique

In this paper, the characteristics of silicon nanocrystals used as charge trapping centers in memory devices are examined using the two-level charge pumping (CP) technique performed as a function of frequency and energy filtered transmission electron microscopy (EFTEM). The parameters extracted from the two methods such as the depth location, density and effective diameter of the nanocrystals are in good quantitative agreement. These results validate the charge pumping approach as a non-destructive powerful technique to access most of the properties of nanocrystals embedded in dielectrics and located at injection distances from the substrate surface not limited to the direct tunneling regime.

Combining elastic and resonant inelastic optical spectroscopies for multiscale probing of embedded nanoparticle architectures

Composite materials consisting of metal nanoparticles (NPs) embedded in a dielectric matrix have a great potential for photonic and plasmonic applications. A set of expensive, time-consuming, and destructive methods (like electron microscopy, electron energy loss, or secondary ion mass spectroscopy) are extensively being used for the structural characterization of such buried NP assemblies. Here, we show the power of combining complementary, noninvasive optical techniques to characterize planar arrays of Ag NPs embedded in a silica film. We use UV-Vis optical reflectivity and resonant Brillouin–Raman scattering, sustained by simulations, to show the sensitivity of these methods to the presence, density, size distribution, and spatial localization of NPs. The accuracy of the results is validated by transmission electron microscopy investigations. Finally the method is applied to obtain images of embedded plasmonic structures from reflectivity and Raman scanning microscopy.