Béatrice Pécassou

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.

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.

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.

Controlled synthesis of buried delta-layers of Ag nanocrystals for near-field plasmonic effects on free surfaces

We report on the shallow synthesis by low energy ion implantation of delta-layers of Ag nanocrystals in SiO2 at few nanometers under its free surface. Transmission electron microscopy observations, ballistic simulations, and reflectance measurements are coupled to define the conditions for which the synthesis is fully controlled and when, on the contrary, this control is lost. We show that low dose implantation leads to the formation of a well-defined single plane of nanocrystals, while for larger doses, sputtering and diffusion effects limit the control of the size, position, and volume amount of these nanocrystals. This paper provides the experimental evidence of the incorporated dose saturation predicted in the literature when implanting metal ions at high doses in glass matrices. Its consequences on the particle population and the plasmonic optical response of the composite layers are carefully analyzed. We show here that this saturation phenomenon is underestimated in standard simulation predictions ...

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 (2.6 eV). 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.

Nanoscale control of Si nanoparticles within a 2D hexagonal array embedded in SiO2 thin films

In this work, we investigate the ability to control Si nanoparticles (NPs) spatially arranged in a hexagonal network of 20 nm wide nanovolumes at controlled depth within SiO2 thin films. To achieve this goal an unconventional lithographic technique was implemented based on a bottom-up approach, that is fully compatible with the existing semiconductor technology. The method combines ultra-low energy ion beam synthesis with nanostructured block-copolymer thin films that are self-assembled on the SiO2 substrates to form a nanoporous template with hexagonally packed pores. A systematic analytical investigation using time of flight-secondary ion mass spectroscopy and low-loss energy filtered transmission electron microscopy demonstrates that by adjusting few fabrication parameters, it is possible to narrow the size distribution of the NPs and to control the number of NPs per nanovolume. Experimental results are critically discussed on the basis of literature data, providing a description of the mechanism involved in the formation of Si NPs.

Structural and magnetic properties of He+ irradiated Co2MnSi Heusler alloys

We have investigated the atomic disorder induced by a 150 keV He+ ion irradiation in a 40 nmthick Co2MnSi Heusler alloy. Disorder parameters on each atomic site are deduced from normal and anomalous X-ray diffraction measurements with Co and CuKasources. While the film grows mainly in the L21 phase with inclusion of B2 grains, we observe an increase of both theMn-Si and Co-Mn exchanges with the ion fluence. HAADF-STEM analysis demonstrates that the increase inMn-Si disorder corresponds to a growing size of the B2 grains while the Co-Mnexchange is accounted for a D03 disorder type in the L21 matrix. These structural modifications are shown to decrease the average magnetization of the alloy, which is due to D03 disorder and local defects induced by irradiation.

Hybrid systems with Ag nanocrystals and Si nanostructures synthesized by ultra-low-energy ion beam synthesis

Hybrid systems based on silicon and silver nanocrystals (Si-NCs and Ag-NCs) are of considerable interest in photon conversion solar cells. Due to their plasmonic properties, Ag-NCs strongly increase the photoluminescence emission intensity of Si-NCs located in their vicinity, allowing, in principle, to solve the problem of their low emission yield. In this work, we have elaborated 2D networks of Ag-NCs and amorphous Si nanoparticles in a controlled way by using Ultra-Low-Energy Ion-Beam-Synthesis. In the proposed synthesis scheme, a 2D layer of Si-NCs is first obtained by implanting Si+ ions at ultra low energy (from 1 to 3 keV) in a SiO2 layer with subsequent high temperature thermal annealing. Then, Ag+ ions are implanted in the same matrix at energies between 3 and 10 keV and crystalline Ag-NCs are formed during the implantation step. Several configurations with either 2D arrays or a large band of Ag-NCs have been obtained following the Ag+ implantation energy. Enhancement of the PL emission from Si na...

The use of biosensors for improving the development of nanotechnology under realistic-use scenarios: Applications for cheaper and more effective silver nanoparticles and nanostructured surfaces

The novel features, based on the exposure of a higher number of atoms on the surfaces, allow nanomaterials to exhibit new or improved features to consumer products, that should be carefully assessed. Here is presented a new method based on the use of biosensors (algal cells) to assess the release of dissolved silver from nanoparticles. Algae were exposed to a) differently coated nanoparticles, b) from nanoparticles differing in their silver content, and c) from nanostructured surfaces differing in the depth at which silver nanoparticles have been embedded. Results shown the importance of chemical coatings, the ratio protein-silver on the AgNP composition and the depth at which are implanted in surfaces, as factors modulating the release of dissolved Ag (i.e. the responsible of the biocide properties of such nanomaterials).