Liquid Phase Isolation of SnS Monolayers with Enhanced Optoelectronic Properties.

Recent advances in atomically thin two dimensional (2D) anisotropic group IVA -VI metal monochalcogenides (MMCs) and their fascinating intrinsic properties and potential applications are hampered due to an ongoing challenge of monolayer isolation. Among the most promising MMCs, tin (II) sulfide (SnS) is an earth-abundant layered material with tunable bandgap and anisotropic physical properties, which render it extraordinary for electronics and optoelectronics. To date, however, the successful isolation of atomically thin SnS single layers at large quantities has been challenging due to the presence of strong interlayer interactions, attributed to the lone-pair electrons of sulfur. Here, a novel liquid phase exfoliation approach is reported, which enables the overcome of such strong interlayer binding energy. Specifically, it demonstrates that the synergistic action of external thermal energy with the ultrasound energy-induced hydrodynamic force in solution gives rise to the systematic isolation of highly crystalline SnS monolayers (1L-SnS). It is shown that the exfoliated 1L-SnS crystals exhibit high carrier mobility and deep-UV spectral photodetection, featuring a fast carrier response time of 400 ms. At the same time, monolayer-based SnS transistor devices fabricated from solution present a high on/off ratio, complemented with a responsivity of 6.7 × 10-3 A W-1 and remarkable stability upon prolonged operation in ambient conditions. This study opens a new avenue for large-scale isolation of highly crystalline SnS and other MMC manolayers for a wide range of applications, including extended area nanoelectronic devices, printed from solution.

Advanced composite glasses with metallic, perovskite, and two-dimensional nanocrystals for optoelectronic and photonic applications.

This article reviews the tremendous advancement of the optoelectronic and photonic properties of inorganic oxide glasses upon the incorporation of metallic, perovskite, and two-dimensional nanocrystals within their matrix. In the first part, we present the exploitation of typical inorganic oxide glasses as hosting platforms for the incorporation of metallic nanoparticles. Such a method offers tremendous advantages in terms of inducing plasmonic features that enable the tunability of the photonic properties of the embedded materials. Along similar lines, due to their exceptional photoluminescence properties all inorganic lead halide perovskites show enormous potential for next generation light-emitting, optoelectronic and photonic devices. To date, however, their usage is limited significantly by their poor chemical stability upon exposure to moisture, and lead toxicity issues. A recent and highly promising approach for overcoming these important challenges is the encapsulation of perovskite nanocrystals within inorganic oxide glasses. Based on this, in the second section we focus on the recent advancements in perovskite glasses in terms of the developed fabrication procedures and the resulting optoelectronic features, while considering the production limitations. In the last part, we consider the development of composite two-dimensional materials glass architectures in terms of the available synthesis routes and the novelty of their optical and emission features. Finally, future perspectives on the described composite glass systems in terms of potential applications are summarized.

Laser-induced topographies enable the spatial patterning of co-cultured peripheral nervous system cells.

The peripheral nervous system comprises glia and neurons that receive the necessary cues for their adhesion and proliferation from their extracellular milieu. In this study, a spatial platform of pseudoperiodic morphologies including patterns of nano- and micro- structures on Si were developed via direct ultrafast-laser structuring and were used as substrates for the patterning of co-cultured neuronal cells. The response of murine Schwann (SW10) and Neuro2a (N2a) cells were investigated both in monocultures and in a glia and neuronal co-culture system. Our results denoted that different types of neural tissue cells respond differently to the underlying topography, but furthermore, the presence of the glial cells alters the adhesion behavior of the neuronal cells in their co-culture. Therefore, we envisage that direct laser structuring that enables spatial patterning of the cells of the nervous system in a controllable manner according to the research needs, could in the future be a useful tool for understanding neural network interfaces and their electrical activity, synaptic processes and myelin formation.

Biofabrication for neural tissue engineering applications.

Unlike other tissue types, the nervous tissue extends to a wide and complex environment that provides a plurality of different biochemical and topological stimuli, which in turn defines the advanced functions of that tissue. As a consequence of such complexity, the traditional transplantation therapeutic methods are quite ineffective; therefore, the restoration of peripheral and central nervous system injuries has been a continuous scientific challenge. Tissue engineering and regenerative medicine in the nervous system have provided new alternative medical approaches. These methods use external biomaterial supports, known as scaffolds, to create platforms for the cells to migrate to the injury site and repair the tissue. The challenge in neural tissue engineering (NTE) remains the fabrication of scaffolds with precisely controlled, tunable topography, biochemical cues, and surface energy, capable of directing and controlling the function of neuronal cells toward the recovery from neurological disorders and injuries. At the same time, it has been shown that NTE provides the potential to model neurological diseases in vitro, mainly via lab-on-a-chip systems, especially in cases for which it is difficult to obtain suitable animal models. As a consequence of the intense research activity in the field, a variety of synthetic approaches and 3D fabrication methods have been developed for the fabrication of NTE scaffolds, including soft lithography and self-assembly, as well as subtractive (top-down) and additive (bottom-up) manufacturing. This article aims at reviewing the existing research effort in the rapidly growing field related to the development of biomaterial scaffolds and lab-on-a-chip systems for NTE applications. Besides presenting recent advances achieved by NTE strategies, this work also delineates existing limitations and highlights emerging possibilities and future prospects in this field.

All-inorganic lead halide perovskite nanohexagons for high performance air-stable lithium batteries.

All-inorganic Cs4PbBr6 perovskite nanohexagons, pre-synthesized by a room temperature co-precipitation method, have been electrochemically investigated in a conventional aqueous electrolyte for potential application as an anode material in Li-ion batteries. The nanohexagons were uniformly deposited on ITO precoated glass substrate and subsequently annealed at ambient air to form a mechanically stable perovskite layer. These perovskite layers showed excellent performance during continuous Li-ion intercalation/deintercalation scans in an aqueous electrolyte, exhibiting a diffusion coefficient of 7.34 × 10-8 cm2 s-1, a specific discharge capacity of 377 mA h g-1, a capacity retention of 75% and coulombic efficiency that deteriorated to 98% after 100 scans. A water-triggered transformation of the Cs4PbBr6 to the CsPb2Br5 was initially observed followed by a reversible Li intercalation/deintercalation in the CsPb2Br5 structure for 40 consecutive scans. Following this period, an irreversible conversion reaction of CsPb2Br5 to CsBr and PbBr2 took place. The excellent electrochemical performance observed is promising towards the potential application of all-inorganic perovskite nanocrystals for air-stable, lithium storage applications.

Ligand-free all-inorganic metal halide nanocubes for fast, ultra-sensitive and self-powered ozone sensors.

Ligand-free all-inorganic lead halide nanocubes have been investigated as ozone sensing materials operating at room temperature. It is found that the nanocubes, crystallined in the orthorhombic CsPbBr3 structure, can operate at room temperature, be self-powered and exhibit high sensitivity and remarkable repeatability. More importantly, they demonstrate higher sensitivity (54% in 187 ppb) and faster response and recovery times compared to hybrid lead mixed halide perovskite (CH3NH3PbI3-x Cl x ) layers, which is the only lead halide perovskite material tested for ozone sensing, to date. Following the exposure to an ozone environment, the stoichiometry and the morphology of the nanocubes remain unaltered. The facile and easy fabrication process together with the high responsivity and stability to the ozone environment makes the bare CsPbBr3 nanocubes a promising material for sensing applications. The sensing properties of the nanoparticulate metal halides presented here provide new exciting opportunities towards engineering reliable and cheap sensing elements for room-temperature operated and self-powered sensors.

Low-temperature benchtop-synthesis of all-inorganic perovskite nanowires.

A facile, low-temperature precipitation-based method is utilized for the synthesis of ultra-thin and highly uniform cesium lead bromide perovskite nanowires (NWs). The reactions facilitate the NWs' crystalline nature over micron-size lengths, while they impart tailored nanowire widths that range from the quantum confinement regime (∼7 nm) down to 2.6 nm. This colloidal synthesis approach is the first of its kind that is carried out on the work-bench, without demanding chemical synthesis equipment. Importantly, the NWs' photoluminescence is shown to improve over time, with no requirement for tedious post-synthesis surface treatment.

Cell patterning via laser micro/nano structured silicon surfaces.

The surface topography of biomaterials can have an important impact on cellular adhesion, growth and proliferation. Apart from the overall roughness, the detailed morphological features, at all length scales, significantly affect the cell-biomaterial interactions in a plethora of applications including structural implants, tissue engineering scaffolds and biosensors. In this study, we present a simple, one-step direct laser patterning technique to fabricate nanoripples and dual-rough hierarchical micro/nano structures to control SW10 cell attachment and migration. It is shown that, depending on the laser processing conditions, distinct cell-philic or cell-repellant patterned areas can be attained with a desired motif. We envisage that our technique could enable spatial patterning of cells in a controllable manner, giving rise to advanced capabilities in cell biology research.

Controlling the morphology and outgrowth of nerve and neuroglial cells: The effect of surface topography.

Unlike other tissue types, like epithelial tissue, which consist of cells with a much more homogeneous structure and function, the nervous tissue spans in a complex multilayer environment whose topographical features display a large spectrum of morphologies and size scales. Traditional cell cultures, which are based on two-dimensional cell-adhesive culture dishes or coverslips, are lacking topographical cues and mainly simulate the biochemical microenvironment of the cells. With the emergence of micro- and nano-fabrication techniques new types of cell culture platforms are developed, where the effect of various topographical cues on cellular morphology, proliferation and differentiation can be studied. Different approaches (regarding the material, fabrication technique, topographical characteristics, etc.) have been implemented. The present review paper aims at reviewing the existing body of literature on the use of artificial micro- and nano-topographical features to control neuronal and neuroglial cells' morphology, outgrowth and neural network topology. The cell responses-from phenomenology to investigation of the underlying mechanisms- on the different topographies, including both deterministic and random ones, are summarized. STATEMENT OF SIGNIFICANCE: There is increasing evidence that physical cues, such as topography, can have a significant impact on the neural cell functions. With the aid of micro-and nanofabrication techniques, new types of cell culture platforms are developed and the effect of surface topography on the cells has been studied. The present review article aims at reviewing the existing body of literature reporting on the use of various topographies to study and control the morphology and functions of cells from nervous tissue, i.e. the neuronal and the neuroglial cells. The cell responses-from phenomenology to investigation of the underlying mechanisms- on the different topographies, including both deterministic and random ones, are summarized.

Laser generated nanoparticles based photovoltaics.

The exploitation of nanoparticles (NP), synthesized via laser ablation in liquids, in photovoltaic devices is reviewed. In particular, the impact of NPs' incorporation into various building blocks within the solar cell architecture on the photovoltaic performance and stability is presented and analysed for the current state of the art photovoltaic technologies.

High steady-state column density of I((2)P3/2) atoms from I2 photodissociation at 532 nm: Towards parity non-conservation measurements.

Steady-state column densities of 10(17) cm(-2) of I((2)P3/2) atoms are produced from photodissociation of I2 vapour at 290.5 K using 5 W of 532 nm laser light. Recombination of the I((2)P3/2) atoms at the cell walls is minimized by coating the cell surface with a hydrophobic silane (dimethyldichlorosilane/DMDCS). Operation at room temperature, and at an I2 vapour pressure of ~0.2 mbar, without using a buffer gas, allows relatively low Lorentz and Doppler widths of ~2π × 1.5 (FWHM) and ~2π × 150 (HW at 1/e(2)) Mrad/s, respectively, at the M1 transition of atomic iodine at 1315 nm. These high column densities and low linewidths are favorable for parity nonconservation optical rotation measurements near this M1 transition. Furthermore, as the cell is completely sealed, this method of production of high-density (127)I((2)P3/2) atoms is also compatible with using iodine radioisotopes, such as for the production of high-density (129)I((2)P3/2).

Spatial non-uniformity in exfoliated WS2 single layers.

Monolayers of transition metal dichalcogenides (TMDs) are atomically thin two-dimensional crystals with attractive optoelectronic properties, which are promising for emerging applications in nanophotonics. Here, we report on the extraordinary spatial non-uniformity of the photoluminescence (PL) and strain properties of exfoliated WS2 monolayers. Specifically, it is shown that the edges of such monolayers exhibit remarkably enhanced PL intensity compared to their respective central area. A comprehensive analysis of the recombination channels involved in the PL process demonstrates a spatial non-uniformity across the monolayer's surface and reflects on the non-uniformity of the intrinsic electron density across the monolayer. Auger electron imaging and spectroscopy studies complemented with PL measurements in different environments indicate that oxygen chemisorption and physisorption are the two fundamental mechanisms responsible for the observed non-uniformity. At the same time Raman spectroscopy analysis shows remarkable strain variations among the different locations of an individual monolayer, however such variations cannot be strictly correlated with the non-uniform PL emission. Our results shed light on the role of the chemical bonding in the competition between exciton complexes in monolayer WS2, providing a method of engineering new nanophotonic functions using WS2 monolayers. It is therefore envisaged that our findings could find diverse applications towards the development of TMD-based optoelectronic devices.

Efficient ternary organic photovoltaics incorporating a graphene-based porphyrin molecule as a universal electron cascade material.

A graphene-based porphyrin molecule (GO-TPP) was synthesized by covalent linkage of graphene oxide (GO) with 5-(4-aminophenyl)-10,15,20-triphenyl porphyrin (TPP-NH2). The yielded graphene-based material is a donor-acceptor (D-A) molecule, exhibiting strong intermolecular interactions between the GO core (A) and the covalently anchored porphyrin molecule (D). To demonstrate the universal role of GO-TPP as an electron cascade material, ternary blend organic photovoltaics based on [6,6]-phenyl-C71-butyric-acid-methyl-ester (PC71BM) as an electron acceptor material and two different polymer donor materials, poly[N-9'-hepta-decanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PCDTBT) and the highly efficient poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7), were fabricated. The addition of GO-TPP into the active layer implies continuous percolation paths between the D-A interfaces, enhancing charge transport, reducing exciton recombination and thus improving the photovoltaic performance of the device. A simultaneous increase of short circuit current density (Jsc), open-circuit voltage (Voc) and fill factor (FF), compared to the PTB7:PC71BM reference cell, led to an improved power conversion efficiency (PCE) of 8.81% for the PTB7:GO-TPP:PC71BM-based device, owing mainly to the more efficient energy level offset between the active layer components.

Data in support on the shape of Schwann cells and sympathetic neurons onto microconically structured silicon surfaces.

This article contains data related to the research article entitled "Laser fabricated discontinuous anisotropic microconical substrates as a new model scaffold to control the directionality of neuronal network outgrowth" in the Biomaterials journal [1]. Scanning electron microscopy (SEM) analysis is performed to investigate whether Schwann cells and sympathetic neurons alter their morphology according to the underlying topography, comprising arrays of silicon microcones with anisotropic geometrical characteristics [1]. It is observed that although soma of sympathetic neurons always preserves its round shape, this is not the case for Schwann cells that become highly polarized in high roughness microconical substrates.

Laser fabricated discontinuous anisotropic microconical substrates as a new model scaffold to control the directionality of neuronal network outgrowth.

Patterning of neuronal outgrowth in vitro is important in tissue engineering as well as for the development of neuronal interfaces with desirable characteristics. To date, this has been achieved with the aid of micro- and nanofabrication techniques giving rise to various anisotropic topographies, either in the form of continuous or discontinuous structures. In this study we propose a currently unexplored geometry of a 3D culture substrate for neuronal cell growth comprising discontinuous subcellular microstructures with anisotropic geometrical cross-section. Specifically, using laser precision 3D micro/nano fabrication techniques, silicon substrates comprising arrays of parallel oriented elliptical microcones (MCs) were fabricated to investigate whether a discontinuous geometry comprising anisotropic features at the subcellular level could influence the alignment of peripheral nervous system cell populations. It was shown that both Schwann cells and axons of sympathetic neurons were parallel oriented onto the MCs of elliptical shape, while they exhibited a random orientation onto the MCs of arbitrary shape. Notably, this topography-induced guidance effect was also observed in more complex cell culture systems, such as the organotypic culture whole dorsal root ganglia (DRG) explants. Our results suggest that a discontinuous topographical pattern could promote Schwann cell and axonal alignment, provided that it hosts anisotropic geometrical features, even though the sizes of those range at the subcellular lengthscale. The laser-patterned arrays of MCs presented here could potentially be a useful platform for patterning neurons into artificial networks, allowing the study of neuronal cells interactions under 3D ex-vivo conditions.

Microconical silicon structures influence NGF-induced PC12 cell morphology.

Micro-and nanofabrication techniques provide the opportunity to develop new types of cell culture platform, where the effect of various topographical cues on cellular functions such as proliferation and differentiation can be studied. In this study, PC12 cells were cultured on patterned silicon (Si) surfaces comprising arrays of microcones (MCs) exhibiting different geometrical characteristics and surface chemistries. It was illustrated that, in the absence of nerve growth factor (NGF), PC12 cells increased proliferation on all types of patterned surface, as compared to flat Si surfaces. However, in the presence of NGF, PC12 cells showed different responses, depending on the plating surface. Unlike low and intermediate rough MC surfaces, highly rough ones exhibiting large distances between MCs did not support PC12 cell differentiation, independently of the MCs' chemical coatings. These results suggest that the geometrical characteristics of MCs alone can influence specific cellular functions. Tailoring of the physical properties of arrays of Si MCs in order to identify which combinations of MC topologies and spatially defined chemistries are capable of driving specific cellular responses is envisaged.

Enhanced field emission of WS2 nanotubes.

Results on electron field emission from free standing tungsten disulfide (WS2) nanotubes (NTs) are presented. Experiments show that the NTs protruding on top of microstructures are efficient cold emitters with turn-on fields as low as 1 V/µm and field enhancement of few thousands. Furthermore, the emission current shows remarkable stability over more than eighteen hours of continuous operation. Such performance and long-term stability of the WS2 cathodes is comparable to that reported for optimized carbon nanotube (CNTs) based emitters. Besides this, it is found that the WS2 cathodes prepared are less sensitive than CNTs in chemical reactive ambients. The high field enhancement and superior reliability achieved indicates a potential for vacuum nanoelectronics and flat panel display applications.

Controlling ripples' periodicity using temporally delayed femtosecond laser double pulses.

We demonstrate the capability to control the ripple periodicity on polycrystalline ZnO films by applying temporally delayed femtosecond double pulses. It is shown that there is a characteristic pulse separation time for which one can switch from low- to high- spatial-frequency ripple formation. Results are interpreted based on the relation of the characteristic delay time with the electron-phonon relaxation time of the material. Our results indicate that temporal pulse shaping can be advantageously used as a mean to control the periodic nanoripples' formation and thus the outcome of laser assisted nanofabrication process, which is desirable for the applications of nanopatterned transparent semiconductors.

Spatially-resolved in-situ structural study of organic electronic devices with nanoscale resolution: the plasmonic photovoltaic case study.

A novel high spatial resolution synchrotron X-ray diffraction stratigraphy technique has been applied in-situ to an integrated plasmonic nanoparticle-based organic photovoltaic device. This original approach allows for the disclosure of structure-property relations linking large scale organic devices to length scales of local nano/hetero structures and interfaces between the different components.

Biomimetic micro∕nanostructured functional surfaces for microfluidic and tissue engineering applications.

This paper reviews our work on the application of ultrafast pulsed laser micro∕nanoprocessing for the three-dimensional (3D) biomimetic modification of materials surfaces. It is shown that the artificial surfaces obtained by femtosecond-laser processing of Si in reactive gas atmosphere exhibit roughness at both micro- and nanoscales that mimics the hierarchical morphology of natural surfaces. Along with the spatial control of the topology, defining surface chemistry provides materials exhibiting notable wetting characteristics which are potentially useful for open microfluidic applications. Depending on the functional coating deposited on the laser patterned 3D structures, we can achieve artificial surfaces that are (a) of extremely low surface energy, thus water-repellent and self-cleaned, and (b) responsive, i.e., showing the ability to change their surface energy in response to different external stimuli such as light, electric field, and pH. Moreover, the behavior of different kinds of cells cultured on laser engineered substrates of various wettabilities was investigated. Experiments showed that it is possible to preferentially tune cell adhesion and growth through choosing proper combinations of surface topography and chemistry. It is concluded that the laser textured 3D micro∕nano-Si surfaces with controllability of roughness ratio and surface chemistry can advantageously serve as a novel means to elucidate the 3D cell-scaffold interactions for tissue engineering applications.