Few-layer and large flake size borophene: preparation with solvothermal-assisted liquid phase exfoliation

The preparation of two-dimensional boron (B) nanosheets, especially for borophene, is still a challenge because of its unique structure and complex B–B bonds in bulk boron. In the present work, a novel preparation technology for borophene with only a few layers and large flake sizes is developed by a solvothermal-assisted liquid phase exfoliation process, consisting of ball milling-thinning, solvothermal swelling, and probe ultrasonic delamination. The exfoliation effect of the bulk B precursors is related to the surface tension and Hildebrand parameter of the selected solvents such as acetone, N,N-dimethyl formamide (DMF), acetonitrile, ethanol, and N-methyl pyrrolidone (NMP), and a relative small surface tension when using solvents is favorable for the exfoliation of bulk B. Four-layer thick borophene and an average lateral size of 5.05 μm can be obtained in acetone as the exfoliating solvent. The surface composition of the exfoliated few-layer borophene with large flake size hardly changes, while the chemical state of B changes to some extent because they are partly oxidized on the surface by contaminates before and after exfoliation. This acetone solvothermal-assisted liquid phase exfoliation technique can be used to prepare high quality borophene with large horizontal sizes, and it will provide the basis to study few-layer borophene with large sizes further.