Photoactive CuI-Cross-Linked Polyurethane Materials.

Using multinuclear copper iodide complexes as cross-linking agents in a polyurethane matrix, original photoluminescent stimuli-responsive materials were synthesized. The intrinsic photoluminescence properties of the covalently incorporated copper iodide complexes are thus transferred to the materials while retaining the beneficial characteristics of the polymer host. The transparent materials exhibit room-temperature phosphorescence with emission switching properties by displaying luminescence thermochromism and solvatochromism. The luminescence thermochromism is characterized by a change in the wavelength and intensity of the emission with temperature, and the vapochromic effect presents a contrasted response of extinction or exaltation according to the nature of the solvent of exposure. By combining the luminescence characteristics of photoactive copper iodide complexes with the ease of polymer processing, the application of these luminescent materials as phosphors in LED (light-emitting diode) devices was also demonstrated. The present study shows that the use of copper iodide complexes as cross-linkers in polymeric materials is a relevant strategy to design materials with enhanced functionalities in addition to their low cost and sustainable characteristics.

Efficient and Facile Synthetic Route of MoO3:MoS2 Hybrid Thin Layer via Oxidative Reaction of MoS2 Nanoflakes.

In the present study, MoO3:MoS2 hybrid thin layers have been synthesized through partial oxidation of MoS2. We have demonstrated that the reaction requires darkness conditions to decrease the oxidation rate, thus obtaining the hybrid, MoO3:MoS2. A simple liquid-phase exfoliation (LPE) is carried out to achieve homogenous MoS2 nanoflakes and high reproducibility of the results after MoS2 oxidation. XPS analyses reveal the presence of MoO3, MoS2, and MoOxSy in the hybrid layer. These results are also confirmed by X-ray diffraction and high-resolution TEM. Optical absorbance reveals that the absorption peaks of the MoO3:MoS2 hybrid are slightly redshifted with the appearance of absorption peaks in the near-infrared region due to the defects created after the oxidation reaction. The composition and atomic percentages of each component in the hybrid layer as a function of reaction time have also been reported to give perspective guides for improving electronic and optoelectronic devices based on 2D-MoS2.

On the Mechanical Performance of Polylactic Material Reinforced by Ceramic in Fused Filament Fabrication.

This study addresses the potential of using ceramics-based filaments as a feedstock material in an additive manufacturing process. Tensile specimens of PLA-ceramic (PLC) material are manufactured using a fused deposition modelling process, applying various printing parameters including printing angle and part orientation. Mechanical testing is performed on both the filaments and 3D-printed parts, and the related engineering quantities are derived. The experimental results show that PLC wire properties are substantially restored for the horizontal and lateral printing orientations, with only a 9% reduction in stiffness. In addition, a typical elastic-plastic response is achieved with these orientations, allowing the PLC to achieve excellent stiffness and elongation-at-break performance. The mechanical performance of the PLC is explained by the large proportion of continuous filaments along the loading direction. In addition, the printing angle is found to be a secondary factor allowing for layups at -45°/+45° and 0°/90°, resulting in the best tensile performance. The downside of using PLC is the lack of mechanical transfer, which is associated with weak interfacial behaviour and the inability to achieve high tensile strength.

Interactions between infernan and calcium: From the molecular level to the mechanical properties of microgels.

With the increasing need for hydrogels with tunable properties for specific biomedical applications, a complete understanding of the structure-function relationship of polymers used for hydrogel development remains crucial for their optimal use. In the present study, by combining experimental and theoretical approaches, the structure-function relationship of a bacterial exopolysaccharide, infernan, displaying both glycosaminoglycan-mimetic and gelling properties, was investigated at molecular and microscopic levels. Atomic force microscopy (AFM) experiments and molecular dynamics simulations were applied to determine the persistence length of individual infernan chains before studying their association induced by calcium. Infernan-based microgels were then produced using microfluidics and their mechanical properties were characterized by AFM methods. The mechanical properties of EPS/calcium microgels were finely tuned by varying the crosslinking density of their network, either by calcium or EPS concentrations. The obtained set of viscoelastic microgels with different elastic modulus values opens several possibilities for their applications in tissue engineering.

Power Conversion Efficiency Improvement of Planar Organic Photovoltaic Cells Using an Original Hybrid Electron-Transporting Layer.

In organic photovoltaic (OPV) cells, besides the organic active layer, the electron-transporting layer (ETL) has a primordial role in transporting electrons and blocking holes. In planar heterojunction-OPVs (PHJ-OPVs), the ETL is called the exciton blocking layer (EBL). The optimum thickness of the EBL is 9 nm. However, in the case of inverted OPVs, such thickness is too high to permit efficient electron collection, due to the fact that there is no possibility of metal diffusion in the EBL during the top metal electrode deposition. In the present work, we show that the introduction of a thin potassium layer between the indium tin oxide (ITO) cathode and the EBL increases dramatically the conductivity of the EBL. We demonstrate that K not only behaves as a simple ultrathin layer allowing for the discrimination of the charge carriers at the cathode/organic material interface but also by diffusing into the EBL, it increases its conductivity by 3 orders of magnitude, which allows us to improve the shape of the J-V characteristics and the PHJ-inverted OPV efficiency by more than 33%. Moreover, we also show that PHJ-inverted OPVs with K in their EBLs are more stable than those with Alq3 alone.

Aggregation-Induced Emission Properties of Copper Iodide Clusters.

The aggregation-induced emission (AIE) properties of two different copper iodide clusters have been studied. These two [Cu4 I4 L4 ] clusters differ by their coordinated phosphine ligand and the luminescent mechanochromic properties are only displayed by one of them. The two clusters are AIE-active luminophors that exhibit an intense emission in the visible region upon aggregation. The formed particles present luminescent thermochromism comparable to that of the bulk compounds. The observed AIE properties can be attributed to suppression of nonradiative relaxation of the excited states in a more rigid state, in relation to the large structural relaxation of the excited triplet state. The differences observed in the AIE properties of the two clusters can be related to the different ligands. A correlation between the luminescence mechanochromic properties and the AIE effect is not straightforward, but the formation of "soft" molecular solids is a common characteristic that can explain the photoactive properties of these compounds.

New airtight transfer box for SEM experiments: Application to lithium and sodium metals observation and analyses.

The surface of some materials reacts very quickly on contact with air, either because it is oxidized or because it gets humidity from the air. For the sake of original surface observation by scanning electron microscopy (SEM), we conceived an airtight transfer box to keep the samples under vacuum from the place of manufacturing to the SEM chamber. This object is designed to fit in all the models of SEM including those provided with an airlock chamber. The design is voluntarily simplified to allow the manufacturing of the object by a standard mechanical workshop. The transfer box can be easily opened by gravity inside the SEM and allows the preservation of the best vacuum inside, before opening. SEM images and energy dispersive spectroscopy (EDX) analyses of metallic lithium and sodium samples are presented prior and after exposure to the air. X-ray Photoelectron Spectroscopy (XPS) analyses of all samples are also discussed in order to investigate the chemical environments of the detected elements.

Direct nanopatterning of polymer/silver nanoblocks under low energy electron beam irradiation.

In this communication, we report on the growth, direct writing and nanopatterning of polymer/silver nanoblocks under low energy electron beam irradiation using a scanning electron microscope. The nanoblocks are produced by placing a droplet of an ethylene glycol solution containing silver nitrate and polyvinylpyrrolidone diluted in ethanol directly on a hot substrate heated up to 150 °C. Upon complete evaporation of the droplet, nanospheres, nano- and micro-triangles and nanoblocks made of silver-containing polymers, form over the substrate surface. Considering the nanoblocks as a model system, we demonstrate that such nanostructures are extremely sensitive to the e-beam extracted from the source of a scanning electron microscope operating at low acceleration voltages (between 5 and 7 kV). This sensitivity allows us to efficiently create various nanopatterns (e.g. arrays of holes, oblique slits and nanotrenches) in the material under e-beam irradiation. In addition to the possibility of writing, the nanoblocks revealed a self-healing ability allowing them to recover a relatively smooth surface after etching. Thanks to these properties, such nanomaterials can be used as a support for data writing and erasing on the nanoscale under low energy electron beam irradiation.

Creating nanoporosity in silver nanocolumns by direct exposure to radio-frequency air plasma.

Nanoporous materials are of great importance for a broad range of applications including catalysis, optical sensors and water filtration. Although several approaches already exist for the creation of nanoporous materials, the race for the development of versatile methods, more suitable for the nanoelectronics industry, is still ongoing. In this communication we report for the first time on the possibility of generating nanoporosity in silver nanocolumns using a dry approach based on the oxidation of silver by direct exposure to a commercially available radio-frequency air plasma. The silver nanocolumns are created by glancing angle deposition using magnetron sputtering of a silver target in pure argon plasma. We show that upon exposure to the rf air plasma, the nanocolumns transform from solid silver into nanoporous silver oxide. We further show that by tuning the plasma pressure and the exposure duration, the oxidation process can be finely adjusted allowing for precisely controlling the morphology and the nanoporosity of the silver oxide nanocolumns. The generation of porosity within the silver nanocolumns is explained according to a cracking-induced oxidation mechanism based on two repeated events occurring alternately during the oxidation process: (i) oxidation of silver upon exposure to the air plasma and (ii) generation of nanocracks and blisters within the oxide layer due to the high internal stress generated within the material during oxidation.

Investigation of hidden periodic structures on SEM images of opal-like materials using FFT and IFFT.

We have developed a method to use fast Fourier transformation (FFT) and inverse fast Fourier transformation (IFFT) to investigate hidden periodic structures on SEM images. We focused on samples of natural, play-of-color opals that diffract visible light and hence are periodically structured. Conventional sample preparation by hydrofluoric acid etch was not used; untreated, freshly broken surfaces were examined at low magnification relative to the expected period of the structural features, and, the SEM was adjusted to get a very high number of pixels in the images. These SEM images were treated by software to calculate autocorrelation, FFT, and IFFT. We present how we adjusted SEM acquisition parameters for best results. We first applied our procedure on an SEM image on which the structure was obvious. Then, we applied the same procedure on a sample that must contain a periodic structure because it diffracts visible light, but on which no structure was visible on the SEM image. In both cases, we obtained clearly periodic patterns that allowed measurements of structural parameters. We also investigated how the irregularly broken surface interfered with the periodic structure to produce additional periodicity. We tested the limits of our methodology with the help of simulated images.

Nanoparticle organization through photoinduced bulk mass transfer.

A series of dipolar triphenylaminoazo derivatives, with largely distinct charge transfer and glass transition temperatures, has been synthesized. Their photomigration capability in the solid state to form surface relief gratings (SRGs) under interferential illumination has been investigated with respect to their photochromic properties and showed a prevailing influence of the bulkiness of the azo substituent. The azo mass transfer was utilized to efficiently photoalign 200 nm polystyrene nanoparticles along the SRG crests, which were initially deposited on nonirradiated azo surfaces. In contrast, nanoparticles spin cast on prestructured surface relief gratings were localized in the troughs of the periodic structures. These distinct locations point out the ability of isotropic and amorphous photochromic thin films to collectively move and organize nano-objects in an ordered fashion through the use of polarized illumination. This versatile approach opens the path to optically aligned ensembles of individual nano-objects over large areas, which can be further combined with metallic conductive or magnetic coating to create novel functional nanostructures.