Polycrystallinity and Stacking in CVD Graphene
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- 作者：Adam W. Tsen ; Lola Brown ; Robin W. Havener ; Jiwoong Park
- 刊名：Accounts of Chemical Research
- 出版年：2013
- 出版时间：October 15, 2013
- 年：2013
- 卷：46
- 期：10
- 页码：2286-2296
- 全文大小：818K
- 年卷期：v.46,no.10(October 15, 2013)
- ISSN：1520-4898
文摘
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 鈥渓ateral junctions,鈥?or grain boundaries between adjacent domains, as well as 鈥渧ertical junctions鈥?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鈥檚 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鈥檚 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.
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 鈥渓ateral junctions,鈥?or grain boundaries between adjacent domains, as well as 鈥渧ertical junctions鈥?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鈥檚 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鈥檚 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.