Chemical Vapor Deposition of Graphene Single Crystals

As a two-dimensional (2D) sp(2)-bonded carbon allotrope, graphene has attracted enormous interest over the past decade due to its unique properties, such as ultrahigh electron mobility, uniform broadband optical absorption and high tensile strength. In the initial research, graphene was isolated from natural graphite, and limited to small sizes and low yields. Recently developed chemical vapor deposition (CVD) techniques have emerged as an important method for the scalable production of large-size and high-quality graphene for various applications. However, CVD-derived graphene is polycrystalline and demonstrates degraded properties induced by grain boundaries. Thus, the next critical step of graphene growth relies on the synthesis of large graphene single crystals. In this Account, we first discuss graphene grain boundaries and their influence on graphene's properties. Mechanical and electrical behaviors of CVD-derived polycrystalline graphene are greatly reduced when compared to that of exfoliated graphene. We then review four representative pathways of pretreating Cu substrates to make millimeter-sized monolayer graphene grains: electrochemical polishing and high-pressure annealing of Cu substrate, adding of additional Cu enclosures, melting and resolidfying Cu substrates, and oxygen-rich Cu substrates. Due to these pretreatments, the nucleation site density on Cu substrates is greatly reduced, resulting in hexagonal-shaped graphene grains that show increased grain domain size and comparable electrical properties as to exfoliated graphene. Also, the properties of graphene can be engineered by its shape, thickness and spatial structure. Thus, we further discuss recently developed methods of making graphene grains with special spatial structures, including snowflakes, six-lobed flowers, pyramids and hexagonal graphene onion rings. The fundamental growth mechanism and practical applications of these well-shaped graphene structures should be interesting topics and deserves more attention in the near future. Following that, recent efforts in fabricating large single-crystal monolayer graphene on other metal substrates, including Ni, Pt, and Ru, are also described. The differences in growth conditions reveal different growth mechanisms on these metals. Another key challenge for graphene growth is to make graphene single crystals on insulating substrates, such as h-BN, SiO2, and ceramic. The recently developed plasma-enhanced CVD method can be used to directly synthesize graphene single crystals on h-BN substrates and is described in this Account as well. To summarize, recent research in synthesizing millimeter-sized monolayer graphene grains with different pretreatments, graphene grain shapes, metal catalysts, and substrates is reviewed. Although great advancements have been achieved in CVD synthesis of graphene single crystals, potential challenges still exist, such as the growth of wafer-sized graphene single crystals to further facilitate the fabrication of graphene-based devices, as well as a deeper understanding of graphene growth mechanisms and growth dynamics in order to make graphene grains with precisely controlled thicknesses and spatial structures.