Xiuyun Zhang

Role of Hydrogen in Graphene Chemical Vapor Deposition Growth on a Copper Surface

Synthesizing bilayer graphene (BLG), which has a band gap, is an important step in graphene application in microelectronics. Experimentally, it was broadly observed that hydrogen plays a crucial role in graphene chemical vapor deposition (CVD) growth on a copper surface. Here, by using ab initio calculations, we have revealed a crucial role of hydrogen in graphene CVD growth, terminating the graphene edges. Our study demonstrates the following. (i) At a low hydrogen pressure, the graphene edges are not passivated by H and thus tend to tightly attach to the catalyst surface. As a consequence, the diffusion of active C species into the area beneath the graphene top layer (GTL) is prohibited, and therefore, single-layer graphene growth is favored. (ii) At a high hydrogen pressure, the graphene edges tend to be terminated by H, and therefore, its detachment from the catalyst surface favors the diffusion of active C species into the area beneath the GTL to form the adlayer graphene below the GTL; as a result, the growth of BLG or few-layer graphene (FLG) is preferred. This insightful understanding reveals a crucial role of H in graphene CVD growth and paves a way for the controllable synthesis of BLG or FLG. Besides, this study also provides a reasonable explanation for the hydrogen pressure-dependent graphene CVD growth behaviors on a Cu surface.

Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition.

Significance Controlled synthesis of wafer-sized single crystalline high-quality graphene is a great challenge of graphene growth by chemical vapor deposition because of the complicated kinetics at edges that govern the growth process. Here we report the synthesis of single-crystal graphene domains with tunable edges from zigzag to armchair via a growth–etching–regrowth process. Both growth and etching of graphene are strongly dependent on the edge structure. This growth/etching behavior is well explained at the atomic level, given the concentrations of kinks on various edges, and allows control of graphene edges and morphology according to the classical kinetic Wulff construction theory. This work provides a deep understanding of the fundamental problems that limit graphene growth by chemical vapor deposition. The controlled growth of large-area, high-quality, single-crystal graphene is highly desired for applications in electronics and optoelectronics; however, the production of this material remains challenging because the atomistic mechanism that governs graphene growth is not well understood. The edges of graphene, which are the sites at which carbon accumulates in the two-dimensional honeycomb lattice, influence many properties, including the electronic properties and chemical reactivity of graphene, and they are expected to significantly influence its growth. We demonstrate the growth of single-crystal graphene domains with controlled edges that range from zigzag to armchair orientations via growth–etching–regrowth in a chemical vapor deposition process. We have observed that both the growth and the etching rates of a single-crystal graphene domain increase linearly with the slanted angle of its edges from 0° to ∼19° and that the rates for an armchair edge are faster than those for a zigzag edge. Such edge-structure–dependent growth/etching kinetics of graphene can be well explained at the atomic level based on the concentrations of the kinks on various edges and allow the evolution and control of the edge and morphology in single-crystal graphene following the classical kinetic Wulff construction theory. Using these findings, we propose several strategies for the fabrication of wafer-sized, high-quality, single-crystal graphene.

Silane-catalysed fast growth of large single-crystalline graphene on hexagonal boron nitride

The direct growth of high-quality, large single-crystalline domains of graphene on a dielectric substrate is of vital importance for applications in electronics and optoelectronics. Traditionally, graphene domains grown on dielectrics are typically only ~1 μm with a growth rate of ~1 nm min−1 or less, the main reason is the lack of a catalyst. Here we show that silane, serving as a gaseous catalyst, is able to boost the graphene growth rate to ~1 μm min−1, thereby promoting graphene domains up to 20 μm in size to be synthesized via chemical vapour deposition (CVD) on hexagonal boron nitride (h-BN). Hall measurements show that the mobility of the sample reaches 20,000 cm2 V−1 s−1 at room temperature, which is among the best for CVD-grown graphene. Combining the advantages of both catalytic CVD and the ultra-flat dielectric substrate, gaseous catalyst-assisted CVD paves the way for synthesizing high-quality graphene for device applications while avoiding the transfer process.

The edges of graphene

The edge of two dimensional (2D) graphene, as the surface of a three dimensional (3D) crystal, plays a crucial role in the determination of its physical, electronic and chemical properties and thus has been extensively studied recently. In this review, we summarize the recent advances in the study of graphene edges, including edge formation energy, edge reconstruction, method of graphene edge synthesis and the recent progress on metal-passivated graphene edges and the role of edges in graphene CVD growth. We expect this review to provide a guideline for readers to gain a clear picture of graphene edges from several aspects, especially the catalyst-passivated graphene edges and their role in graphene CVD growth.

Formation and Healing of Vacancies in Graphene Chemical Vapor Deposition (CVD) Growth

The formation and kinetics of single and double vacancies in graphene chemical vapor deposition (CVD) growth on Cu(111), Ni(111), and Co(0001) surfaces are investigated by the first-principles calculation. It is found that the vacancies in graphene on the metal surfaces are dramatically different from those in free-standing graphene. The interaction between the vacancies and the metal surface and the involvement of a metal atom in the vacancy structure greatly reduce their formation energies and significantly change their diffusion barriers. Furthermore, the kinetic process of forming vacancies and the potential route of their healing during graphene CVD growth on Cu(111) and Ni(111) surfaces are explored. The results indicate that Cu is a better catalyst than Ni for the synthesis of high-quality graphene because the defects in graphene on Cu are formed in a lower concentration and can be more efficiently healed at the typical experimental temperature. This study leads to a deep insight into the atomic process of graphene growth, and the mechanism revealed in this study can be used for the experimental design of high-quality graphene synthesis.