The epitaxial growth of single-crystal thin films relies on the availability of a single-crystal substrate and a strong interaction between epilayer and substrate. Previous studies have reported the roles of the substrate (e.g., symmetry and lattice constant) in determining the orientations of chemical vapor deposition (CVD)-grown graphene, and Cu( 111) is considered as the most promising substrate for epitaxial growth of graphene single crystals. However, the roles of gas-phase reactants and graphene−substrate interaction in determining the graphene orientation are still unclear. Here, we find that trace amounts of oxygen is capable of enhancing the interaction between graphene edges and Cu(111) substrate and, therefore, eliminating the misoriented graphene domains in the nucleation stage. A modified anomalous grain growth method is developed to improve the size of the as-obtained Cu(111) single crystal, relying on strongly textured polycrystalline Cu foils. The batch-to-batch production of A3-size (∼0.42 × 0.3 m 2 ) single-crystal graphene films is achieved on Cu(111) foils relying on a self-designed pilot-scale CVD system. The as-grown graphene exhibits ultrahigh carrier mobilities of 68 000 cm 2 V −1 s −1 at room temperature and 210 000 cm 2 V −1 s −1 at 2.2 K. The findings and strategies provided in our work would accelerate the mass production of high-quality misorientation-free graphene films.

Since its first successful isolation over a decade ago, academic and industrial interest has triggered the steady progress of the commercialization of graphene, as evidenced by a wealth of graphene-related patents, products, institutes, and startups. Among currently available graphene materials, graphene films derived from chemical vapor deposition (CVD) techniques, with fine controllability and uniformity, have been proven to be a promising candidate for various applications, with exciting demonstrations in electronics, optoelectronics, sensors, and filtering membrane. In this review, recent progress toward the commercialization of CVD films is summarized, covering the state-of-the-art methods for controllable synthesis, up-scale technologies for mass production, and demonstrations in potential commercial applications, which will propel the successful commercialization of graphene films by transforming the laboratory-scale advances. Moreover, a brief summary of the current market of CVD graphene films is provided with regarding to the commercial graphene products and production equipment. Finally, a perspective on the critical challenges and future direction of CVD graphene films will be presented.