Designing all graphdiyne materials as graphene derivatives: topologically driven modulation of electronic properties

TL;DR

This study systematically generates and analyzes 26 graphdiyne structures derived from graphene, revealing how topology and structure influence stability and electronic properties, guiding the design of new 2D carbon materials.

Contribution

The paper introduces an algorithm to generate diverse graphdiyne structures and analyzes their stability and electronic properties based on topology and carbon hybridization.

Findings

Relative energies increase with sp/sp2 ratio, following topology-dependent trends.

Topologies influence electronic behavior, producing semiconductors, zero-gap semiconductors, or metals.

Topological effects can guide the design of new 2D carbon materials.

Abstract

Designing new 2D systems with tunable properties is an important subject for science and technology. Starting from graphene, we developed an algorithm to systematically generate 2D carbon crystals belonging to the family of graphdiynes (GDYs) and having different structures and sp/sp2 carbon ratio. We analyze how structural and topological effects can tune the relative stability and the electronic behavior, to propose a rationale for the development of new systems with tailored properties. A total of 26 structures have been generated, including the already known polymorphs such as {\alpha}-, \b{eta}- and {\gamma}-GDY. Periodic density functional theory calculations have been employed to optimize the 2D crystal structures and to compute the total energy, the band structure, and the density of states. Relative energies with respect to graphene have been found to increase when the values of carbon sp/sp2 ratio increase, following however different trends based on the peculiar topologies present in the crystals. These topologies also influence the band structure giving rise to semiconductors with a finite bandgap, zero-gap semiconductors displaying Dirac cones, or metallic systems. The different trends allow identifying some topological effects as possible guidelines in the design of new 2D carbon materials beyond graphene.