Blue Phosphorene Bilayer Is a Two-Dimensional Metal and an Unambiguous Classification Scheme for Buckled Hexagonal Bilayers

High-level first-principles computations predict blue phosphorene bilayer to be a two-dimensional metal. This structure has not been considered before and was identified by employing a block-diagram scheme that yields the complete set of five high-symmetry stacking configurations of buckled honeycomb layers, and allows their unambiguous classification. We show that all of these stacking configurations are stable or at least metastable both for blue phosphorene and gray arsenene bilayers. For blue phosphorene, the most stable stacking arrangement has not yet been reported, and surprisingly it is metallic, while the others are indirect band gap semiconductors. As it is impossible to interchange the stacking configurations by translations, all of them should be experimentally accessible via the transfer of monolayers. The metallic character of blue phosphorene bilayer is caused by its short interlayer distance of 3.01 Å and offers the exceptional possibility to design single elemental all-phosphorus transistors.