The electronic and spintronic properties of the monovacancies in freestanding and isotopically compressed graphene are investigated using hybrid exchange density functional perturbation theory. When the effects of electronic self-interaction are taken into account, an integer magnetic moment of 2 μB is identified for a Jahn-Teller reconstructed V1(5-9) monovacancy in freestanding graphene. For graphene with stable ripples induced by a compressive strain of 5%, a bond reconstruction produces a V1(55-66) structure for the monovacancy, which is localized at the saddle points of the ripple. The sizeable local distortion induced by reconstruction modifies both the geometric and electronic properties of rippled graphene and quenches the magnetic moment of the vacancy due to the sp3 hybridization of the central atom. The nonmagnetic V1(55-66) structure is found to be stable on rippled structures, with the formation energy ∼2.3 eV lower than that of the metastable distorted V1(5-9) structures localized at sites other than the saddle points. The electronic ground state of distorted V1(5-9) corresponds to a wide range of fractional magnetic moments (0.50-1.25 μB). The computed relative stabilities and the electronic and magnetic properties of the V1(5-9) structures are found to be closely related to their local distortions. This analysis of the fundamental properties of defective graphene under compression suggests a number of strategies for generating regular defect patterns with tuneable magnetic and electronic properties and may, therefore, be used as a novel technique to achieve more precise control of graphene electronic structure for various application scenarios such as transistors, strain sensors, and directed chemisorption.
© 2022 The Authors. Published by American Chemical Society.