Surface Functionalization of Black Phosphorus via Potassium toward High-Performance Complementary Devices

Two-dimensional black phosphorus configured field-effect transistor devices generally show a hole-dominated ambipolar transport characteristic, thereby limiting its applications in complementary electronics. Herein, we demonstrate an effective surface functionalization scheme on few-layer black phosphorus, through in situ surface modification with potassium, with a view toward high performance complementary device applications. Potassium induces a giant electron doping effect on black phosphorus along with a clear bandgap reduction, which is further corroborated by in situ photoelectron spectroscopy characterizations. The electron mobility of black phosphorus is significantly enhanced to 262 (377) cm² V^-1 s^-1 by over 1 order of magnitude after potassium modification for two-terminal (four-terminal) measurements. Using lithography technique, a spatially controlled potassium doping technique is developed to establish high-performance complementary devices on a single black phosphorus nanosheet, for example, the p-n homojunction-based diode achieves a near-unity ideality factor of 1.007 with an on/off ratio of ∼10⁴. Our findings coupled with the tunable nature of in situ modification scheme enable black phosphorus as a promising candidate for further complementary electronics.