Solution-Phase Bulk Synthesis of Covalently Functionalized Black Phosphorus Nanosheets

Abstract

Phosphorene—a two-dimensional layered semiconductor derived from the exfoliation of black phosphorus (BP)—is attracting significant interest in the nanomaterials community due to its high charge-carrier mobility, tunable bandgap, and anisotropic properties, but suffers rapid degradation upon exposure to ambient conditions. Herein we demonstrate the stabilization of phosphorene nanosheets via controlled chemical modification with organic azides, a relatively mild pathway towards covalent functionalization of the phosphorene surface, allowing for greater control over surface functionalization while preventing destructive phosphorene oxidation. Treated phosphorene exhibits a remarkable increase in ambient stability versus untreated phosphorene. This method offers further potential for the controlled, rational design of highly-tunable phosphorene-based materials using fundamental phosphorus chemistry as a guide.