Electronic Transport of MoS2 Monolayered Flakes Investigated by Scanning Electrochemical Microscopy.

The amazing properties of 2D materials are envisioned to revolutionize several domains such as flexible electronics, electrocatalysis, or biosensing. Herein we introduce scanning electrochemical microscopy (SECM) as a tool to investigate molybdenum disulfide in a straightforward fashion, providing localized information regarding the electronic transport within chemical vapor deposition (CVD)-grown crystalline MoS2 single layers having micrometric sizes. Our investigations show that within flakes assemblies some flakes are well electrically interconnected, with no detectable contact resistance, whereas others are not electrically connected at all, independent of the size of the physical contact between them. Overall, the work shows how the complex electronic behavior of MoS2 flake assemblies (semiconducting nature, contact quality between flakes) can be investigated with SECM.

Scalable Disordered Hyperuniform Architectures via Nanoimprint Lithography of Metal Oxides.

Fabrication and scaling of disordered hyperuniform materials remain hampered by the difficulties in controlling the spontaneous phenomena leading to this novel kind of exotic arrangement of objects. Here, we demonstrate a hybrid top-down/bottom-up approach based on sol-gel dip-coating and nanoimprint lithography for the faithful reproduction of disordered hyperuniform metasurfaces in metal oxides. Nano- to microstructures made of silica and titania can be directly printed over several cm2 on glass and on silicon substrates. First, we describe the polymer mold fabrication starting from a hard master obtained via spontaneous solid-state dewetting of SiGe and Ge thin layers on SiO2. Then, we assess the effective disordered hyperuniform character of master and replica and the role of the thickness of the sol-gel layer on the metal oxide replicas and on the presence of a residual layer underneath. Finally, as a potential application, we show the antireflective character of titania structures on silicon. Our results are relevant for the realistic implementation over large scales of disordered hyperuniform nano- and microarchitectures made of metal oxides, thus opening their exploitation in the framework of wet chemical assembly.

Carbon nanotube columns for flow systems: influence of synthesis parameters.

Flow reactors are expected to play an increasingly important role in the production of chemicals. A simple carbon-based scaffold to easily develop flow systems is here detailed. Using a chemical vapour deposition technique, the controlled in situ growth of vertically aligned (VA) multi-wall carbon nanotubes (MWCNTs) into quartz columns with 2 mm inner diameter is achieved. Several of the described MWCNT columns (CNCs) can be produced at a time. The influence of synthesis parameters on the formation of these VA-MWCNT scaffolds is reported and discussed (e.g. injection time of the precursor, carrier gas flow rate, inner diameter and length of the quartz column, position in the furnace during synthesis). Raman spectroscopy, optical microscopy, scanning and transmission electron microscopy are used to assess the coverage of the inner channel of the quartz column with VA-MWCNTs and their overall quality. The length of the CNCs together with the carrier gas flow rate are found to be key parameters to control the MWCNT length profile within the CNCs. Fluoresceinamine molecules and platinum nanoparticles are successfully immobilised within these MWCNT scaffolds. The benefits of the CNCs for flow system design are summarised as the controlled filling with MWCNTs makes the detailed CNCs versatile scaffolds for flow catalysis and filtration.

Bimodal Porosity and Stability of a TiO2 Gig-Lox Sponge Infiltrated with Methyl-Ammonium Lead Iodide Perovskite.

We created a blend between a TiO2 sponge with bimodal porosity and a Methyl-Ammonium Lead Iodide (MAPbI3) perovskite. The interpenetration of the two materials is effective thanks to the peculiar sponge structure. During the early stages of the growth of the TiO2 sponge, the formation of 5-10 nm-large TiO2 auto-seeds is observed which set the micro-porosity (<5 nm) of the layer, maintained during further growth. In a second stage, the auto-seeds aggregate into hundreds-of-nm-large meso-structures by their mutual shadowing of the grazing Ti flux for local oxidation. This process generates meso-pores (10-100 nm) treading across the growing layer, as accessed by tomographic synchrotron radiation coherent X-ray imaging and environmental ellipsometric porosimetry. The distributions of pore size are extracted before (>47% V) and after MAPbI3 loading, and after blend ageing, unfolding a starting pore filling above 80% in volume. The degradation of the perovskite in the blend follows a standard path towards PbI2 accompanied by the concomitant release of volatile species, with an activation energy of 0.87 eV under humid air. The use of dry nitrogen as environmental condition has a positive impact in increasing this energy by ~0.1 eV that extends the half-life of the material to 7 months under continuous operation at 60 °C.

Environment-controlled sol-gel soft-NIL processing for optimized titania, alumina, silica and yttria-zirconia imprinting at sub-micron dimensions.

Metal oxide (MOX) surface nanopatterns can be prepared using Soft-Nano-Imprint-Lithography (soft-NIL) combined with sol-gel deposition processing. Even if sol-gel layers remain gel-like straight after deposition, their accurate replication from a mould remains difficult as a result of the fast evaporation-induced stiffening that prevents efficient mass transfer underneath the soft mould. The present work reports a detailed investigation of the role of the xerogel layer conditioning (temperature and relative humidity) prior to imprinting and its influence on the quality of the replication. This study is performed on four different systems namely titania, alumina, silica and yttria-stabilised zirconia. We demonstrate that the quality of the replica can be considerably improved without the use of sacrificial stabilising organic agents, but by simply applying an optimal aging at controlled temperature and relative humidity specific to each different reported MOX. In each case this condition corresponds to swelling the initial xerogels of around 30%vol by water absorption from humidity. We show that this degree of swelling represents the best compromise for sufficiently increasing the xerogel fluidity while limiting the shrinkage upon final thermal curing.

Full Investigation of Angle Dependence in Dip-Coating Sol-Gel Films.

Dip-coating is one of the most convenient methods used in laboratory and industry to deposit a solid layer onto a surface with a controlled thickness from a chemical solution. The present Article investigates the influence of the withdrawal speed on the film thickness and homogeneity with respect to the dipping angle ranging from 90° (conventional vertical configuration) to 1° (quasi-horizontal configuration). Several advantages were found in the latter extreme low-dipping angle conditions that are (i) an available wider range of thickness, (ii) the elimination of the perturbations/effects induced by evaporation, and (iii) the compatibility with large surface and single face deposition at high throughput and using a minimal amount of solution. One shows that experimental data follow the Landau-Levich model, modified by Tallmadge for angle dependence, only for intermediate regimes of speed. A maximal thickness limited by the physical-chemical characteristics of the initial solution is reached at high speeds while a minimal thickness, corresponding to a single layer of solute interacting with the substrate surface can be obtained at very low speeds.

Complex dewetting scenarios of ultrathin silicon films for large-scale nanoarchitectures.

Dewetting is a ubiquitous phenomenon in nature; many different thin films of organic and inorganic substances (such as liquids, polymers, metals, and semiconductors) share this shape instability driven by surface tension and mass transport. Via templated solid-state dewetting, we frame complex nanoarchitectures of monocrystalline silicon on insulator with unprecedented precision and reproducibility over large scales. Phase-field simulations reveal the dominant role of surface diffusion as a driving force for dewetting and provide a predictive tool to further engineer this hybrid top-down/bottom-up self-assembly method. Our results demonstrate that patches of thin monocrystalline films of metals and semiconductors share the same dewetting dynamics. We also prove the potential of our method by fabricating nanotransfer molding of metal oxide xerogels on silicon and glass substrates. This method allows the novel possibility of transferring these Si-based patterns on different materials, which do not usually undergo dewetting, offering great potential also for microfluidic or sensing applications.