Abstract

Exfoliation of two-dimensional (2D) nanosheets from three-dimensional (3D) non-layered, non-van der Waals crystals represents an emerging strategy for materials engineering that could significantly increase the library of 2D materials. Yet, the exfoliation mechanism in which nanosheets are derived from crystals that are not intrinsically layered remains unclear. Here, we show that planar defects in the starting 3D boron material promote the exfoliation of 2D boron sheets—by combining liquid-phase exfoliation, aberration-corrected scanning transmission electron microscopy, Raman spectroscopy, and density functional theory calculations. We demonstrate that 2D boron nanosheets consist of a planar arrangement of icosahedral sub-units cleaved along the {001} planes of β-rhombohedral boron. Correspondingly, intrinsic stacking faults in 3D boron form parallel layers of faulted planes in the same orientation as the exfoliated nanosheets, reducing the {001} cleavage energy. Planar defects represent a potential engineerable pathway for exfoliating 2D sheets from 3D boron and, more broadly, the other covalently bonded materials.