Application of a Cryo-FIB-SEM-µRaman Instrument to Probe the Depth of Vitreous Ice in a Frozen Sample.

The development of instruments combining multiple characterization and imaging tools drove huge advances in material science, engineering, biology, and other related fields. Notably, the coupling of SEM with micro-Raman spectrometry (µRaman) provides the means for the correlation between structural and physicochemical properties at the surface, while dual focused ion beam (FIB)-scanning electron microscopes (SEMs) operating under cryogenic conditions (cryo-FIB-SEM) allow for the analysis of the ultrastructure of materials in situ and in their native environment. In cryo-FIB-SEM, rapid and efficient methods for assessing vitrification conditions in situ are required for the accurate investigation of the original structure of hydrated samples. This work reports for the first time the use of a cryo-FIB-SEM-µRaman instrument to efficiently assess the accuracy of cryo-fixation methods. Analyses were performed on plunge-freezed highly hydrated calcium phosphate cement (CPC) and a gelatin composite. By making a trench of a defined thickness with FIB, µRaman analyses were carried out at a specific depth within the frozen material. Results show that the µRaman signal is sensitive to the changes in the molecular structures of the aqueous phase and can be used to examine the depth of vitreous ice in frozen samples. The method presented in this work provides a reliable way to avoid imaging artifacts in cryo-FIB-SEM that are related to cryo-fixation and therefore constitutes great interest in the study of vitreous materials exhibiting high water content, regardless of the sample preparation method (i.e., by HPF, plunge freezing, and so on).

Intense Raman D Band without Disorder in Flattened Carbon Nanotubes.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

Silica based ionogels: interface effects with aprotic and protic ionic liquids with lithium.

In the frame of the development of solid ionogel electrolytes with enhanced ion transport properties, this paper investigates ionogel systems constituted by ∼80 wt% of ionic liquids (ILs) confined in meso-/macroporous silica monolith materials. The anion-cation coordination for two closely related ILs, either aprotic (AIL) butylmethylpyrrolidinium or protic (PIL) butylpyrrolidinium, both with bis(trifluoromethylsulfonyl)imide (TFSI) anions, with and without lithium cations, is studied in depth. The ILs are confined within silica with well-defined mesoporosities (8 to 16 nm). The effects of this confinement, onto melting points, onto conductivity followed by impedance spectroscopy, and onto lithium-TFSI coordination followed by Raman spectroscopy, are presented. Opposite effects have been observed on the melting temperature: it increased for the AIL (+2 °C) upon confinement, while it decreased for the PIL (-2 °C). With lithium, the confinement led to an increase of the melting temperature (+1 °C) for the PIL and AIL. Regarding ionic conductivities, a relative maximum was observed at 40 °C for a mesopore diameter of 10 nm for the AIL with 0.5 M lithium, while it was not clearly visible for the PIL. These differences are discussed in view of the charge balance at the interface between silanols and ILs: the presence of a PIL, contrary to an AIL, is expected to modify the acidity of the silica. Raman data showed that the coordination number of lithium by TFSI is reduced upon AIL confinement, although this was not observed for PILs. At last, this work highlights the impact of the acidity of a PIL on the chemistry occurring at the interface of the host network within ionogels.

AFM-Nano Manipulation of Plasmonic Molecules Used as "Nano-Lens" to Enhance Raman of Individual Nano-Objects.

This paper explores the enhancement of Raman signals using individual nano-plasmonic structures and demonstrates the possibility to obtain controlled gold plasmonic nanostructures by atomic force microscopy (AFM) manipulation under a confocal Raman device. By manipulating the gold nanoparticles (Nps) while monitoring them using a confocal microscope, it is possible to generate individual nano- structures, plasmonic molecules not accessible currently by lithography at these nanometer scales. This flexible approach allows us to tune plasmonic resonance of the nanostructures, to generate localized hot spots and to circumvent the effects of strong electric near field gradients intrinsic to Tip Enhanced Raman Spectroscopy (TERS) or Surface Enhanced Raman Spectroscopy (SERS) experiments. The inter Np distances and symmetry of the plasmonic molecules in interaction with other individual nano-objects control the resonance conditions of the assemblies and the enhancement of their Raman responses. This paper shows also how some plasmonic structures generate localized nanometric areas with high electric field magnitude without strong gradient. These last plasmonic molecules may be used as "nano-lenses" tunable in wavelength and able to enhance Raman signals of neighbored nano-object. The positioning of one individual probed nano-object in the spatial area defined by the nano-lens becomes then very non-restrictive, contrary to TERS experiments where the spacing distance between tip and sample is crucial. The experimental flexibility obtained in these approaches is illustrated here by the enhanced Raman scatterings of carbon nanotube.

Growth of low doped monolayer graphene on SiC(0001) via sublimation at low argon pressure.

Silicon carbide (SiC) sublimation is the most promising option to achieve transfer-free graphene at the wafer-scale. We investigated the initial growth stages from the buffer layer to monolayer graphene on SiC(0001) as a function of annealing temperature at low argon pressure (10 mbar). A buffer layer, fully covering the SiC substrate, forms when the substrate is annealed at 1600 °C. Graphene formation starts from the step edges of the SiC substrate at higher temperature (1700 °C). The spatial homogeneity of the monolayer graphene was observed at 1750 °C, as characterized by Raman spectroscopy and magneto-transport. Raman spectroscopy mapping indicated an AG-graphene/AG-HOPG ratio of around 3.3%, which is very close to the experimental value reported for a graphene monolayer. Transport measurements from room temperature down to 1.7 K indicated slightly p-doped samples (p ≃ 1010 cm-2) and confirmed both continuity and thickness of the monolayer graphene film. Successive growth processes have confirmed the reproducibility and homogeneity of these monolayer films.

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.

Correction: Enhancing carrier generation in TiO2 by a synergistic effect between plasmon resonance in Ag nanoparticles and optical interference.

Correction for 'Enhancing carrier generation in TiO2 by a synergistic effect between plasmon resonance in Ag nanoparticles and optical interference' by Giuseppe Cacciato et al., Nanoscale, 2015, 7, 13468-13476.

Enhancing carrier generation in TiO2 by a synergistic effect between plasmon resonance in Ag nanoparticles and optical interference.

Silver nanoparticles have been embedded at a few nanometer distance from the free surface of titania/silica multilayers using low energy ion beam synthesis. Transmission electron microscopy shows the presence of 3 nm-sized crystalline particles. Reflectance spectroscopy on these composite substrates shows an increase of the light capture efficiency in the visible range. This behaviour is interpreted as a synergistic effect between plasmon polariton resonance and Fabry-Perot interferences. Plasmon-resonant Raman spectroscopy is deeply used to analyze, on one hand confinement of vibrations and electronic excitations in Ag NPs, and on the other hand coupling of polar TiO2 phonons with injected photo-generated carriers. It is shown how these new Ag/TiO2 nanocomposite films appear as very promising to enhance the efficiency and enlarge the spectral sensitivity of plasmo-electronics devices.

Vibrational and electronic excitations in gold nanocrystals.

An experimental analysis of all elementary excitations--phonons and electron-holes--in gold nanocrystals has been performed using plasmon resonance Raman scattering. Assemblies of monodisperse, single-crystalline gold nanoparticles, specific substrates and specific experimental configurations have been used. Three types of excitations are successively analyzed: collective quasi-acoustical vibrations of the particles (Lamb's modes), electron-hole excitations (creating the so-called "background" in surface-enhanced Raman scattering) and ensembles of atomic vibrations ("bulk" phonons). The experimental vibrational density of states extracted from the latter contribution is successfully compared with theoretical estimations performed using atomic simulations. The dominant role of surface atoms over the core ones on lattice dynamics is clearly demonstrated. Consequences on the thermodynamic properties of nanocrystals such as the decrease of the characteristic Debye temperature are also considered.

Three dimensional design of silver nanoparticle assemblies embedded in dielectrics for Raman spectroscopy enhancement and dark-field imaging.

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.