Onset of vertical bonds in new GaN multilayers: beyond van der Waals solids

A suspended single layer of GaN in a honeycomb structure is stable in a planar geometry. By stacking these GaN layers one can construct bilayers or multilayers, even new three-dimensional (3D) periodic structures. In this study, we clarified how the planar layers are buckled with the onset of vertical Ga-N bonds. Among the four stable phases of bilayer GaN, only one of them maintains the planar geometry, which is bound by weak van der Waals interactions. For the remaining three phases, the layers are buckled with the onset of weak vertical bonds, and attain total energies slightly lower than that of the planar geometry. Structural phase changes, as well as direct-indirect band transitions take place under strain and electrostatic charging. The vertical bonds become shorter in multilayers, and eventually attain the bulk value. Among the stable phases of 3D periodic GaN, only one with a graphite-like structure behaves as a layered, van der Waals solid; whereby others are 3D uniform crystals beyond the van der Waals solid.