Resolving the Structural Duality of Graphene Grain Boundaries

Abstract

Abstract Grain boundaries (GBs) are ubiquitous in large‐scale graphene samples, playing a crucial role in their overall performance. Due to their complexity, they are usually investigated as model structures, under the assumption of a fully relaxed interface. Here, cantilever‐based non‐contact atomic force microscopy (ncAFM) is presented as a suitable technique to resolve, atom by atom, the complete structure of these linear defects. These experimental findings reveal a richer scenario than expected, with the coexistence of energetically stable and metastable graphene GBs. Although both GBs are structurally composed of pentagonal and heptagonal rings, they can be differentiated by the irregular geometric shapes present in the metastable boundaries. Theoretical modeling and simulated ncAFM images, accounting for the experimental data, show that metastable GBs form under compressive uniaxial strain and exhibit vertical corrugation, whereas stable GBs remain in a fully relaxed, flat configuration. By locally introducing energy with the AFM tip, the possibility of manipulating the metastable GBs, driving them toward their minimum energy configuration, is shown. Notably, the high‐resolution ncAFM images reveal a clear dichotomy: while the structural distortions of metastable grain boundaries are confined to just a few atoms, their impact on graphene's properties extends over significantly larger length scales.