Fluorination‐Enhanced Ambient Stability and Electronic Tolerance of Black Phosphorus Quantum Dots

The environmental instability and uneliminable electronic trap states in black phosphorus quantum dots (BPQDs) limit the optoelectronics and related applications of BPQDs. Here, fluorinated BPQDs (F‐BPQDs) are successfully synthesized by using a facile electrochemical exfoliation and synchronous fluorination method. The F‐BPQDs exhibit robust ambient stability and limited fluorination capability, showing a nonstoichiometric fluorination degree ( D F ) maximum of ≈0.68. Density functional theory calculations confirm that due to the edge etching effect of fluorine adatoms, the simulated F‐BPQDs become structurally unstable when D F surpasses the limit. Furthermore, the trap states of BPQDs can be effectively eliminated via fluorination to obtain a coordination number of 3 or 5 for fluorinated and unfluorinated phosphorus atoms. The results reveal that the air‐stable F‐BPQDs exhibit fluorine defect‐enhanced electronic tolerance, which is crucial for nanophotonics and nanoelectronics applications.