Defect activated optical Raman modes in single layer MoSe2.

In the last decade, transition metal dichalcogenides (TMDs) have been intensively synthesized/studied thus linking their morphological aspect to their physical properties, and consequently leading to the understanding of the possible benefits of defects in such materials. Nevertheless, for future applications, quantifying and identifying defects in TMDs is still a milestone to reach in order to better employ these materials in optoelectronic devices. Raman Spectroscopy has been successfully employed in graphene to quantify punctual or line defects. In this paper, we bombarded monolayer MoSe2with He ions and found out the existence of three defect activated Raman bands around 250-300 cm-1. Density functional theory calculations were employed to obtain the electronic and phonon dispersion bands, making it possible to infer that these bands arise from inter-valley Raman double resonance processes. Interestingly, the same punctual defect model, that allows one to predict the defect concentration at which graphene starts to become amorphous, also works for TMDs. Hence, this work opens the door to the macroscopic quantification of defects in TMDs, which is essential for technological applications.

Mechanical properties of thin glassy polymer films filled with spherical polymer-grafted nanoparticles.

It is commonly accepted that the addition of spherical nanoparticles (NPs) cannot simultaneously improve the elastic modulus, the yield stress, and the ductility of an amorphous glassy polymer matrix. In contrast to this conventional wisdom, we show that ductility can be substantially increased, while maintaining gains in the elastic modulus and yield stress, in glassy nanocomposite films composed of spherical silica NPs grafted with polystyrene (PS) chains in a PS matrix. The key to these improvements are (i) uniform NP spatial dispersion and (ii) strong interfacial binding between NPs and the matrix, by making the grafted chains sufficiently long relative to the matrix. Strikingly, the optimal conditions for the mechanical reinforcement of the same nanocomposite material in the melt state is completely different, requiring the presence of spatially extended NP clusters. Evidently, NP spatial dispersions that optimize material properties are crucially sensitive to the state (melt versus glass) of the polymeric material.

Synthesis of Organic Semiconductor Nanoparticles with Different Conformations Using the Nanoprecipitation Method.

In recent years, nanoparticulate materials have aroused interest in the field of organic electronics due to their high versatility which increases the efficiency of devices. In this work, four different stable conformations based on the organic semiconductors P3HT and PC71BM were synthesized using the nanoprecipitation method, including blend and core-shell nanoparticles. All nanoparticles were obtained free of surfactants and in aqueous suspensions following the line of ecologically correct routes. The structural and optoelectronic properties of the nanoparticles were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-visible absorption spectroscopy and UV-visible photoluminescence (PL). Even in aqueous media, the blend and core-shell nanoparticles exhibited a greater light absorption capacity, and these conformations proved to be effective in the process of dissociation of excitons that occurs at the P3HT donor/PC71BM acceptor interface. With all these characteristics and allied to the fact that the nanoparticles are surfactant-free aqueous suspensions, this work paves the way for the use of these colloids as a photoactive layer of organic photovoltaic devices that interface with biological systems.

Ecological Biosubstrates Obtained from Onion Pulp (Allium cepa L.) for Flexible Organic Light-Emitting Diodes.

A new biopolymer obtained from onion pulp (Allium cepa L.) was employed to produce a sustainable substrate for flexible organic light-emitting diodes (FOLEDs). Indium tin oxide (ITO) and SiO2 thin films were deposited by rf-magnetron sputtering onto these biosubstrates to obtain flexible, transparent, and conductive anodes, on top of which FOLEDs were produced. This new biomaterial exhibits an optical transparency of 63% at 550 nm. ITO films were optimized by varying rf power during deposition onto the biopolymers, and their electrical properties are comparable to the those of ITO grown on top of rigid substrates: a carrier concentration of -3.63 × 1021 cm-3 and carrier mobility of 7.72 cm2 V-1 s-1 for the optimized film. Consequently, the sheet resistance and resistivity of this ITO film were 8.92 Ω sq-1 and 2.23 × 10-4 Ω cm, respectively, hence allowing the production of FOLEDs. The A. cepa L. based FOLED was fabricated using CuPc, ß-NPB, and Alq3 as organic layers, and it exhibited a maximum luminance of about 2062 cd m-2 at 16.6 V. The current efficiency reached a maximum value of 2.1 cd A-1 at 85.3 mA cm-2. The obtained results suggest the possibility to use these substrates for innovative biocompatible applications in optoelectronics, such as photodynamic therapy.

Giant and Tunable Anisotropy of Nanoscale Friction in Graphene.

The nanoscale friction between an atomic force microscopy tip and graphene is investigated using friction force microscopy (FFM). During the tip movement, friction forces are observed to increase and then saturate in a highly anisotropic manner. As a result, the friction forces in graphene are highly dependent on the scanning direction: under some conditions, the energy dissipated along the armchair direction can be 80% higher than along the zigzag direction. In comparison, for highly-oriented pyrolitic graphite (HOPG), the friction anisotropy between armchair and zigzag directions is only 15%. This giant friction anisotropy in graphene results from anisotropies in the amplitudes of flexural deformations of the graphene sheet driven by the tip movement, not present in HOPG. The effect can be seen as a novel manifestation of the classical phenomenon of Euler buckling at the nanoscale, which provides the non-linear ingredients that amplify friction anisotropy. Simulations based on a novel version of the 2D Tomlinson model (modified to include the effects of flexural deformations), as well as fully atomistic molecular dynamics simulations and first-principles density-functional theory (DFT) calculations, are able to reproduce and explain the experimental observations.

Effect of graphene oxide on bacteria and peripheral blood mononuclear cells.

BACKGROUND: Driven by the potential biological applications of graphene, many groups have studied the response of cells exposed to graphene oxide (GO). In particular, investigations of bacteria indicate that there are 2 crucial parameters, which so far have only been investigated separately: GO size and exposure methodology. Our study took into account both parameters. We carefully characterized the samples to catalog sizes and structural properties, and tested different exposure methodologies: exposure in saline solution and in the presence of growth media. Furthermore, we performed experiments with peripheral blood mononuclear cells exposed to our GO materials. METHODS: Atomic force microscopy, scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the morphology and composition of different samples of GO: GO-H2O, GO-PBS and GO-MG. Our samples had 2D sizes of ~100 nm (GO-H2O and GO-PBS) and >2 µm (GO-MG). We tested antibacterial activity and cytotoxicity toward peripheral blood mononuclear cells of 3 different GO samples. RESULTS: A size-dependent growth inhibition of Escherichia coli (DH5 α) in suspension was found, which proved that this effect depends strongly on the protocol followed for exposure. Hemocompatibility was confirmed by exposing peripheral blood mononuclear cells to materials for 24 hours; viability and apoptosis tests were also carried out. CONCLUSIONS: Our experiments provide vital information for future applications of GO in suspension. If its antibacterial properties are to be potentiated, care should be taken to select 2D sizes in the micrometer range, and exposure should not be carried out in the presence of grow media.

Tuning Localized Surface Plasmon Resonance in Scanning Near-Field Optical Microscopy Probes.

A reproducible route for tuning localized surface plasmon resonance in scattering type near-field optical microscopy probes is presented. The method is based on the production of a focused-ion-beam milled single groove near the apex of electrochemically etched gold tips. Electron energy-loss spectroscopy and scanning transmission electron microscopy are employed to obtain highly spatially and spectroscopically resolved maps of the milled probes, revealing localized surface plasmon resonance at visible and near-infrared wavelengths. By changing the distance L between the groove and the probe apex, the localized surface plasmon resonance energy can be fine-tuned at a desired absorption channel. Tip-enhanced Raman spectroscopy is applied as a test platform, and the results prove the reliability of the method to produce efficient scattering type near-field optical microscopy probes.