Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement.
16 August 2016 in Angewandte Chemie International Edition
We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few‐layer antimonene by liquid‐phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few‐layer antimonene suitable for on‐surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high‐quality few‐layer antimonene nanosheets with large lateral dimensions. These nanolayers are extremely stable under ambient conditions. Their Raman signals are strongly thickness‐dependent, which was rationalized by means of density functional theory calculations.
Herein, we have developed a systematic study on the oxidation and passivation of mechanically exfoliated black phosphorus (BP). We analyzed the strong anisotropic behavior of BP by scanning Raman microscopy providing an accurate method for monitoring the oxidation of BP via statistical Raman spectroscopy. Furthermore, different factors influencing the environmental instability of the BP, i.e., thickness, lateral dimensions or visible light illumination, have been investigated in detail. Finally, we discovered that the degradation of few-layer BP flakes of <10 nm can be suppressed for months by using ionic liquids, paving the way for the development of BP-based technologies.
20 October 2016 in Angewandte Chemie International Edition