Stacking-dependent structural and electronic properties of trilayer γ-graphyne: An approach for new 2D carbon allotropes

Abstract Vertical stacks of two-dimensional (2D) materials with interlayer van der Waals (vdW) force have provided a versatile approach for creating hybrid materials and modulating various properties. In this work, the structural and electronic properties of trilayer γ-graphyne, involving different stacking patterns, have been investigated through first-principles approaches. The result indicates that a metal-to-semiconducting transition can be triggered simply by switching the stacking order of trilayer γ-graphyne. More interestingly, in addition to typical vdW homostructures, new 2D carbon allotropes with novel carbon networks can be achieved on the basis of trilayer γ-graphyne, arising from the absence of intralayer acetylene linkages during the structural relaxation. One of the new 2D carbon allotropes possesses an intrinsic semiconducting nature with a wide bandgap of 1.827 eV, coupled with superior structural stability beyond single-layer γ-graphyne. Moreover, the biaxial strain effect on the new 2D carbon allotrope, as well as the trilayer vdW stacks, has also been revealed in this work. Correspondingly, the in-plane tensile strain is demonstrated to further enlarge the electronic bandgaps in these carbon sheets. Therefore, the results of this work imply the great potential of few-layer graphyne in future carbon-based nanoelectronic devices, and simultaneously provide a new approach for developing and synthesizing novel 2D carbon allotropes via the vertical stacking of graphyne with inherent acetylene linkages.