Synthesis of bilayer borophene

As the nearest-neighbour element to carbon, boron is theoretically predicted to have a planar two-dimensional form, named borophene, with novel properties, such as Dirac fermions and superconductivity. Several polymorphs of monolayer borophene have been grown on metal surfaces, yet thicker bilayer and few-layer nanosheets remain elusive. Here we report the synthesis of large-size, single-crystalline bilayer borophene on the Cu(111) surface by molecular beam epitaxy. Combining scanning tunnelling microscopy and first-principles calculations, we show that bilayer borophene consists of two stacked monolayers that are held together by covalent interlayer boron-boron bonding, and each monolayer has β12-like structures with zigzag rows. The formation of a bilayer is associated with a large transfer and redistribution of charge in the first boron layer on Cu(111), which provides additional electrons for the bonding of additional boron atoms, enabling the growth of the second layer. The bilayer borophene is shown to possess metallic character, and be less prone to being oxidized than its monolayer counterparts.