Atomically Thin Arsenene and Antimonene: Semimetal–Semiconductor and Indirect–Direct Band‐Gap Transitions

Abstract The typical two‐dimensional (2D) semiconductors MoS 2 , MoSe 2 , WS 2 , WSe 2 and black phosphorus have garnered tremendous interest for their unique electronic, optical, and chemical properties. However, all 2D semiconductors reported thus far feature band gaps that are smaller than 2.0 eV, which has greatly restricted their applications, especially in optoelectronic devices with photoresponse in the blue and UV range. Novel 2D mono‐elemental semiconductors, namely monolayered arsenene and antimonene, with wide band gaps and high stability were now developed based on first‐principles calculations. Interestingly, although As and Sb are typically semimetals in the bulk, they are transformed into indirect semiconductors with band gaps of 2.49 and 2.28 eV when thinned to one atomic layer. Significantly, under small biaxial strain, these materials were transformed from indirect into direct band‐gap semiconductors. Such dramatic changes in the electronic structure could pave the way for transistors with high on/off ratios, optoelectronic devices working under blue or UV light, and mechanical sensors based on new 2D crystals.