Realization of an Ideal Cairo Tessellation in Nickel Diazenide NiN₂: High-Pressure Route to Pentagonal 2D Materials

Abstract

Most of the studied two-dimensional (2D) materials are based on highly symmetric hexagonal structural motifs. In contrast, lower-symmetry structures may have exciting anisotropic properties leading to various applications in nanoelectronics. In this work we report the synthesis of nickel diazenide NiN₂ which possesses atomic-thick layers comprised of Ni₂N₃ pentagons forming Cairo-type tessellation. The layers of NiN₂ are weakly bonded with the calculated exfoliation energy of 0.72 J/m², which is just slightly larger than that of graphene. The compound crystallizes in the space group of the ideal Cairo tiling (<i>P</i>4/<i>mbm</i>) and possesses significant anisotropy of elastic properties. The single-layer NiN₂ is a direct-band-gap semiconductor, while the bulk material is metallic. This indicates the promise of NiN₂ to be a precursor of a pentagonal 2D material with a tunable direct band gap.