Scalable synthesis of high-quality graphene via roll-to-roll chemical vapor deposition faces a fundamental conflict between rapid growth and crystallographic perfection. Conventional methane (CH₄)-derived growth suffers from disordered nucleation and orientation mismatch at elevated precursor pressures, limiting industrial adoption. This work resolves this challenge by employing acetylene (C₂H₂) as a carbon precursor to enable carbon dimer-mediated cyclotrimerization nucleation. First-principles calculations reveal that C₂H₂-derived carbon dimers (C₂) spontaneously assemble into hexagonal nuclei, bypassing defect-prone chain-to-ring transitions inherent to monatomic carbon pathway of CH₄. This mechanism ensures > 98% lattice orientation consistency even at nucleation densities of 10⁴ mm⁻², in stark contrast to CH₄-derived graphene. Crucially, the enhanced surface adsorption of C₂ species enables continuous nucleation during lateral growth, achieving high growth rate of 500 mm·min⁻¹ at roll-to-roll process. Leveraging dimeric carbon precursors and Cu single-crystallization technique, we demonstrate roll-to-roll production of graphene films with high crystallographic orientation across meter-scale Cu(111) foils. This precursor-specific strategy decouples nucleation density from disorder accumulation, establishing a scalable pathway for industrial graphene manufacturing.

Multilayer graphene films demonstrate superior electrical and thermal conductivity, mechanical properties, and barrier performance compared to monolayer, thereby exhibiting greater potential for industrial applications. However, the synthesis of multilayer graphene films continues to face critical challenges, primarily including uncontrollable layer numbers, incomplete understanding of growth mechanisms, and poor reproducibility and scalability in mass production. This study introduces the “fractional layer” concept and corresponding mathematical model to precisely quantify graphene layers for the first time. Using this metric, we systematically established growth principles and process windows for layer-controlled graphene synthesis on copper substrates and elucidated the multilayer growth mechanism governed by modulating the lateral growth and vertical growth kinetics. Based on this theoretical framework, the continuous preparation of 2.3-layer graphene films was achieved via industrial scale roll-to-roll chemical vapor deposition equipment, exhibiting exceptional macroscopic uniformity and demonstrating significant potential for applications in transparent, flexible electrothermal heaters. Our work will establish a solid material foundation for the industrial application of multilayer graphene films and offer novel insights into the layer-controlled synthesis of other two-dimensional materials.

Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize high-quality graphene films, and low-temperature growth of defect-free graphene films is long-term challenged because of the high energy barrier for precursor dissociation and graphitization. Reducing the growth temperature can also bring advantages on wrinkle-free graphene films owing to the minimized thermal expansion coefficient mismatch. This work focuses on density functional theory (DFT) calculations of the carbon source precursor with hydroxyl group, especially CH₃OH, on low-temperature CVD growth of graphene on Cu and CuNi substrate. We calculated all the possible cleavage paths for CH₃OH on transition metal substrates. The results show that, firstly, the cleavage barriers of CH₃OH on transition metal substrates are slightly lower than those of CH₄, and once CO appears, it is difficult to break the C–O bond. Secondly, the CO promotes a better formation and retention of perfect rings in the early stage of graphene nucleation and reduces the edge growth barriers. Thirdly, these deoxidation barriers of CO are reduced after CO participates in graphene edge growth. This paper provides a strategy for the low-temperature growth of wrinkles-free graphene on transition metal substrates using CH₃OH.

Carbon source precursor is a critical factor governing chemical vapor deposition growth of graphene films. Methane (CH₄), has been the most commonly used precursor in the last decade, but it presents challenges in terms of decomposition efficiency and growth rate. Here we thoroughly evaluated acetylene (C₂H₂), a precursor that is probably for providing carbon dimer (C₂) species, for fast growth of large-scale graphene films. We find that the graphene growth behaviors fueled by C₂H₂ exhibit unconventional localized growth behavior with significant advantages in terms of high growth rate, which mainly ascribe to the as-decomposed C₂ species. Therefore, a C₂-fueled scanning growth strategy is proposed, and the fast scanning growth rate of 40 cm/min was experimentally demonstrated. This growth strategy is compatible with the approach of unidirectional growth of single-crystal graphene films, and the as-grown graphene films are of high-quality. This work demonstrates a reliable and promising strategy for the rapid synthesis of high-quality graphene film and may pave the avenue to cost-effective mass production of graphene materials in the roll-to-roll system.

Chemical vapor deposition (CVD) in conjunction with batch-to-batch manufacturing process is considered as the most promising technical route for mass-production of high-quality graphene films. To improve the space utilization of the CVD chamber and increase the throughput per batch, stacking of the Cu foil substrates is efficient, but suffers from the problems of adjacent fusion and the poor mass-transfer. Here, we demonstrate an efficient strategy for high-throughput and rapid growth of high-quality graphene by alternate stacking of Cu foils and porous carbon fiber paper (CFP). Relying on the unhindered mass-transfer through the pores of CFPs, full-covered high-quality graphene films on compact-stacked Cu foils were achieved within 2 min. Computational fluid dynamics (CFD) simulation and isotope labeling technique were performed to explore the gas diffusion and graphene growth process in the confined space of the Cu-CFP stacks. This work provides a feasible method for industrial production of graphene films, which may also be used for batch production of other two-dimensional materials.