A novel liquid-phase exfoliation of layered crystals enables the production of defect-free and high quality 2D-crystal dispersions on a large scale.
Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of β-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g L . Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. It is demonstrated that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few micrometers, and thicknesses ranging from 1 to 20 nm, with a maximum population centered at ≈5 nm, corresponding to 4 Se-In-In-Se quaternary layers. It is also shown that no formation of further InSe-based compounds (such as In Se ) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for the hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. The dependence of the InSe flakes' morphologies, i.e., surface area and thickness, on the HER performances is highlighted, achieving the best efficiencies with small flakes offering predominant edge effects. The theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes.
The liquid-phase exfoliation (LPE) of black phosphorus (BP) is a strategic route for the large-scale production of phosphorene and few-layer BP (FL-BP) flakes. The exploitation of this exfoliated material in cutting-edge technologies, e.g., in flexible electronics and energy storage, is however limited by the fact that the LPE of BP is usually carried out at a high boiling point and in toxic solvents. In fact, the solvent residual is detrimental to device performance in real applications; thus, complete solvent removal is critical. Here, we tackle these issues by exfoliating BP in different lowboiling-point solvents. Among these solvents, we find that acetone also provides a high concentration of exfoliated BP, leading to the production of FL-BP flakes with an average lateral size and thickness of ∼30 and ∼7 nm, respectively. The use of acetone to produce less defective few-layer BP flakes (FL-BP acetone ) from bulk crystals is a straightforward process which enables the rapid preparation of homogeneous thin films thanks to the fast solvent evaporation. The ratio of edge to bulk atoms for the BP flakes here produced, combined with the use of low-boiling-point solvents for the exfoliation process, suggests that these thin films are promising anodes for lithium-ion batteries. To this end, we tested Li-ion half cells with FL-BP acetone anodes achieving a reversible specific capacity of 480 mA h g −1 at a current density of 100 mA g −1 , over 100 charge/discharge cycles. Moreover, a reversible specific capacity of 345 mA h g −1 is achieved for the FL-BP acetone -based anode at high current density (i.e., 1 A g −1 ). These findings indicate that the FL-BP acetone -based battery is promising with regards to the design of fast charge/ discharge devices. Overall, the presented process is a step forward toward the fabrication of phosphorene-based devices.
Layered semiconductors of the IIIA-VIA group have attracted considerable attention in (opto)electronic applications thanks to their atomically thin structures and their thickness-dependent optical and electronic properties, which promise ultrafast response and high sensitivity. In particular, 2D indium selenide (InSe) has emerged as a promising candidate for the realization of thin-film field effect transistors and phototransistors due to its high intrinsic mobility (>10 2 cm 2 V −1 s −1 ) and the direct optical transitions in an energy range suitable for visible and near-infrared light detection. A key requirement for the exploitation of large-scale (opto)electronic applications relies on the development of low-cost and industrially relevant 2D material production processes, such as liquid phase exfoliation, combined with the availability of high-throughput device fabrication methods. Here, a β polymorph of indium selenide (β-InSe) is exfoliated in isopropanol and spray-coated InSe-based photodetectors are demonstrated, exhibiting high responsivity to visible light (maximum value of 274 A W −1 under blue excitation 455 nm) and fast response time (15 ms). The devices show a gate-dependent conduction with an n-channel transistor behavior.Overall, this study establishes that liquid phase exfoliated β-InSe is a valid candidate for printed high-performance photodetectors, which is critical for the development of industrial-scale 2D material-based optoelectronic devices.
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