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Anomalous doping effect in black phosphorene from first-principles calculations

Using first-principles density functional theory calculations, we investigate the geometries, electronic structures, and thermodynamic stabilities of substitutionally doped phosphorene sheets with group III, IV, V, and VI elements. We find that the electronic properties of phosphorene are drastically modified by the number of valence electrons in dopant atoms. The dopants with even number of valence electrons enable the doped phosphorenes to have a metallic feature, while the dopants with odd number of valence electrons keep the semiconducting feature with a larger band gap than the undoped phosphorene. This even-odd behavior is attributed to the peculiar bonding characteristics of phosphorene and the strong hybridization of sp orbitals between dopants and phosphorene. The calculated formation energies of various substitutional dopants in phosphorene show that such doped systems can be thermodynamically stable.