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[资源] Acc. Chem. Res.最新综述:化学气相沉积法合成的石墨烯的多晶和堆积

最新一期的Acc. Chem. Res.刊发了美国康奈尔大学Jiwoong Park课题组撰写的题为Polycrystallinity and Stacking in CVD Graphene的研究性综述,主要讲述了化学气相沉积(CVD)法合成的石墨烯存在的多晶现象和堆积方式,以及多晶石墨烯/多层石墨烯相关的性质。文章11页,引文37篇。

Graphene, a truly two-dimensional hexagonal lattice of carbon atoms, possesses remarkable properties not seen in any other material, including ultrahigh electron mobility, high tensile strength, and uniform broadband optical absorption. While scientists initially studied its intrinsic properties with small, mechanically exfoliated graphene crystals found randomly, applying this knowledge would require growing large-area films with uniform structural and physical properties. The science of graphene has recently experienced revolutionary change, mainly due to the development of several large-scale growth methods. In particular, graphene synthesis by chemical vapor deposition (CVD) on copper is a reliable method to obtain films with mostly monolayer coverage. These films are also polycrystalline, consisting of multiple graphene crystals joined by grain boundaries. In addition, portions of these graphene films contain more than one layer, and each layer can possess a different crystal orientation and stacking order.

In this Account, we review the structural and physical properties that originate from polycrystallinity and stacking in CVD graphene. To begin, we introduce dark-field transmission electron microscopy (DF-TEM), a technique which allows rapid and accurate imaging of key structural properties, including the orientation of individual domains and relative stacking configurations. Using DF-TEM, one can easily identify “lateral junctions,” or grain boundaries between adjacent domains, as well as “vertical junctions” from the stacking of graphene multilayers. With this technique, we can distinguish between oriented (Bernal or rhombohedral) and misoriented (twisted) configurations.

The structure of lateral junctions in CVD graphene is sensitive to growth conditions and is reflected in the material’s electrical and mechanical properties. In particular, grain boundaries in graphene grown under faster reactant flow conditions have no gaps or overlaps, unlike more slowly grown films. These structural differences can affect the material’s electrical properties: for example, better-connected grain boundaries are more electrically conductive. However, grain boundaries in general are mechanically weaker than pristine graphene, which is an order of magnitude stronger than CVD graphene based on indentation measurements performed with an atomic force microscope.

Vertical junctions in multilayer CVD graphene have two key structural features. First, bilayer graphene (BLG) with Bernal stacking exists in two mirrored configurations (AB or AC) that also form isolated domains. Similarly, oriented trilayer graphene also has alternating ABA and ABC stacked layers. Second, in twisted multilayer graphene, stacked layers lack long-range atomic registry and can move freely relative to each other, which generates unique optical properties. In particular, an interlayer optical excitation produces strong Raman and absorption peaks, dependent on the twist angle.

A better understanding of the structural and physical properties of grain boundaries and multilayers in CVD graphene is central to realizing the full potential of graphene in large-scale applications. In addition, these studies provide a model for characterizing other layered materials, such as hexagonal boron nitride and MoS2, where similar polycrystallinity and stacking are expected when grown in large areas.

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