Synthesis of Black Phosphorene Quantum Dots from Red Phosphorus

Black phosphorene quantum dots (BPQDs) are most commonly derived from high-cost black phosphorus, while previous syntheses from the low-cost red phosphorus (P_red) allotrope are highly oxidised. Herein, we present an intrinsically scalable method to produce high quality BPQDs, by first ball-milling P_red to create nanocrystalline P_black and subsequent reductive etching using lithium electride solvated in liquid ammonia. The resultant ~25 nm BPQDs are crystalline with low oxygen content, and spontaneously soluble as individualized monolayers in tertiary amide solvents, as directly imaged by liquid-phase transmission electron microscopy. This new method presents a scalable route to producing quantities of high quality BPQDs for academic and industrial applications.