Synchronous and Unidirectional Epitaxy of Layer‐Controlled Graphene on Oxidized Single‐Crystal Copper Wafers With Tunable Stacking Order

ABSTRACT The deterministic synthesis of wafer‐scale two‐dimensional (2D) materials with programmable layer number, crystallographic orientation, and stacking order is essential for unlocking their layer‐dependent quantum properties and enabling scalable device integration. Here, we demonstrate a synchronous and unidirectional epitaxy strategy for chemical vapor deposition growth of layer‐controlled graphene on atomically flat oxidized single‐crystal Cu wafers. Using a Cu(111)–Cu 2 O(111) heterogeneous catalytic substrate, we achieved 2‐inch single‐crystalline graphene films with precisely tunable layer numbers (2 to 5). By engineering the atomic steps of high‐index Cu surfaces, we created deterministic spatial patterning of alternating Bernal and rhombohedral stacking in trilayer graphene, as confirmed by near‐field nano‐optics and angle‐resolved photoemission spectroscopy. The resulting wafer‐scale films exhibit exceptional thickness uniformity, high crystallinity, and an ultra‐flat surface. This work provides a unified growth framework that concurrently resolves the intertwined challenges of layer control, wafer‐scale single crystallinity, and stacking order modulation, laying a material foundation for advanced device studies and potential applications.