Interfacial Coupling Induced Discrete Orientation of Epitaxial Graphene on High‐Index Cu Substrates

Abstract Controlled and precise synthesis of materials has been a central pursuit in academia and industry. With the rise of twistronics research, there is growing demand for synthesizing orientation‐controlled 2D materials with atomic precision. Previous theories for 2D materials can predict graphene (Gr) growth on low‐index metal substrates but fail to explain the discrete orientations on most high‐index substrates, inconsistent with experimental data. Using density functional theory (DFT) and ab‐initio molecular dynamics (AIMD), this study explores graphene growth on high‐index substrates, showing that atomic steps do not dominate in trapping C atoms or driving preferential graphene nucleation at high temperatures. Thus, the possibility of intrinsic atomic steps in inducing graphene orientation on high‐index substrates is ruled out. Interfacial coupling strength between graphene and substrates is quantified using a close contact index (CCI), linking atomic structure and electronic states. The coupling between graphene and high‐index Cu surfaces is generally weak, reducing substrate anchoring and increasing graphene orientation dispersion. The extension of this theory to bilayer graphene (BLG) reveals competition between Gr/Cu interfacial coupling and Gr/Gr interlayer coupling, offering insights for controlling twist angles. This theory explains the discrete orientations on high‐index substrates, providing a theoretical basis for synthesizing orientation‐controlled graphene.