Metal‐Ion‐Modified Black Phosphorus with Enhanced Stability and Transistor Performance

Black phosphorus (BP), a burgeoning elemental 2D semiconductor, has aroused increasing scientific and technological interest, especially as a channel material in field-effect transistors (FETs). However, the intrinsic instability of BP causes practical concern and the transistor performance must also be improved. Here, the use of metal-ion modification to enhance both the stability and transistor performance of BP sheets is described. Ag⁺ spontaneously adsorbed on the BP surface via cation-π interactions passivates the lone-pair electrons of P thereby rendering BP more stable in air. Consequently, the Ag⁺ -modified BP FET shows greatly enhanced hole mobility from 796 to 1666 cm² V^-1 s^-1 and ON/OFF ratio from 5.9 × 10⁴ to 2.6 × 10⁶ . The mechanisms pertaining to the enhanced stability and transistor performance are discussed and the strategy can be extended to other metal ions such as Fe³⁺ , Mg²⁺ , and Hg²⁺ . Such stable and high-performance BP transistors are crucial to electronic and optoelectronic devices. The stability and semiconducting properties of BP sheets can be enhanced tremendously by this novel strategy.