High‐Mobility p‐Type and n‐Type Copper Nitride Semiconductors by Direct Nitriding Synthesis and In Silico Doping Design

: Thin-film photovoltaics (PV) have emerged as a technology that can meet the growing demands for efficient and low-cost large-scale cells. However, the photoabsorbers currently in use contain expensive or toxic elements, and the difficulty in bipolar doping, particularly in a device structure, requires elaborate optimization of the heterostructures for improving the efficiency. This study shows that bipolar doping with high hole and electron mobilities in copper nitride (Cu3 N), composed solely of earth-abundant and environmentally benign elements, is readily available through a novel gaseous direct nitriding reaction applicable to uniform and large-area deposition. A high-quality undoped Cu3 N film is essentially an n-type semiconductor, while p-type conductivity is realized by interstitial fluorine doping, as predicted using density functional theory calculations and directly proven by atomically resolved imaging. The synthetic methodology for high-quality p-type and n-type films paves the way for the application of Cu3 N as an alternative absorber in thin-film PV.