Influence of dopants on the impermeability of graphene

Graphene has attracted much attention as an impermeable membrane and a protective coating against oxidation. While many theoretical studies have shown that defect-free graphene is impermeable, in reality graphene inevitably has defects in the form of grain boundaries and vacancies. Here, we study the effects of N-dopants on the impermeability of few-layered graphene (FLG) grown on copper using chemical vapor deposition. The grain boundaries in FLG have minimal impact on their permeability to oxygen as they do not provide a continuous channel for gas transport due to high tortuosity. However, we experimentally show that the N-dopants in FLG display multiple configurations that create structural imperfections to selectively allow gas molecules to permeate. We used a comprehensive array of tools including Raman spectroscopy, X-ray photoelectron spectroscopy, optically stimulated electron emission measurements, and density functional theory of N-doped graphene on copper to elucidate the effects of dopant configuration on the impermeability of graphene. Our results clearly show that oxygen can permeate through graphene with non-graphitic nitrogen dopants that create pores in graphene and oxidize the underlying Cu substrate while graphitic nitrogen dopants do not show any changes compared to the pristine form. Furthermore, we observed that the work function of graphene can be tuned effectively by changing the dopant configuration.