Exfoliation of black phosphorus in ionic liquids

We report the characterization and formation of sonication-assisted liquid phase exfoliation of bulk black phosphorus (BP) crystals with the incorporation of two representative ionic liquids (ILs) ([Emim][Tf₂N] and [Bmim][Tf₂N]) as green dispersing media was attempted, which resulted in stable dispersion of multi-layer BP flakes with unsuspected high oxidation resistance and chemical/structural integrity due to the presence of IL layer on top of BP flakes. There are two unveiled issues for the generation of BP dispersion in ILs. First, thin films of BP flakes can be simply prepared through our approach. Because self-oxidation of BP in ambient condition can be significantly minimized in ILs, vacuum filtration step can be adopted to produce BP thin films in ambient condition. Second, the binding of IL molecules on BP flakes has been firstly demonstrated by the time-of-flight secondary ion mass spectrometry characterization. In addition to the exploitation of ILs as the green solvents with less environmental harmfulness, IL-based exfoliation of BP might be easily scalable because harsh control of atmospheric oxygen and moisture is unnecessary in this approach.