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.

Two-dimensional nanomaterials such as MoS 2 are of great interest both because of their novel physical properties and their applications potential. Liquid exfoliation, an important production method, is limited by our inability to quickly and easily measure nanosheet size, thickness or concentration. Here we demonstrate a method to simultaneously determine mean values of these properties from an optical extinction spectrum measured on a liquid dispersion of MoS 2 nanosheets. The concentration measurement is based on the size-independence of the low-wavelength extinction coefficient, while the size and thickness measurements rely on the effect of edges and quantum confinement on the optical spectra. The resultant controllability of concentration, size and thickness facilitates the preparation of dispersions with pre-determined properties such as high monolayer-content, leading to first measurement of A-exciton MoS 2 luminescence in liquid suspensions. These techniques are general and can be applied to a range of two-dimensional materials including WS 2 , MoSe 2 and WSe 2 .

While liquid exfoliation is a powerful technique to produce defect-free nanosheets in large quantities, its usefulness is limited by broad nanosheet thickness distributions and low monolayer contents. Here we demonstrate liquid processing techniques, based on iterative centrifugation cascades, which can be designed to achieve either highly efficient nanosheet size-selection and/or monolayer enrichment. The resultant size-selected dispersions were used to establish quantitative metrics to determine monolayer volume fraction, as well as mean nanosheet size and thickness, from standard spectroscopic measurements. Such metrics allowed us to design and optimize centrifugation cascades to enrich liquid exfoliated WS2 dispersions up to monolayer contents of 75%. Monolayer-rich dispersions show relatively bright photoluminescence with narrow line widths (<35 meV) indicating the high quality of the nanosheets. The enriched dispersions display extinction spectra with distinct features, which also allow the direct estimation of monolayer contents.