Large-area single-crystal sheets of borophene on Cu(111) surfaces

Borophene, a theoretically proposed two-dimensional (2D) boron allotrope^1-3, has attracted much attention^4,5 as a candidate material platform for high-speed, transparent and flexible electronics^6-9. It was recently synthesized, on Ag(111) substrates^10,11, and studied by tunnelling and electron spectroscopy¹². However, the exact crystal structure is still controversial, the nanometre-size single-crystal domains produced so far are too small for device fabrication and the structural tunability via substrate-dependent epitaxy is yet to be proven. We report on the synthesis of borophene monitored in situ by low-energy electron microscopy, diffraction and scanning tunnelling microscopy (STM) and modelled by ab initio theory. We resolved the crystal structure and phase diagram of borophene on Ag(111), but found that the domains remain nanoscale for all growth conditions. However, by growing borophene on Cu(111) surfaces, we obtained large single-crystal domains, up to 100 μm² in size. The crystal structure is a novel triangular network with a concentration of hexagonal vacancies of η = 1/5. Our experimental data, together with first principles calculations, indicate charge-transfer coupling to the substrate without significant covalent bonding. Our work sets the stage for fabricating borophene-based devices and substantiates the idea of borophene as a model for development of artificial 2D materials.