Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil

Huang, Ming; Bakharev, Pavel V.; Wang, Zhujun; Biswal, Mandakini; Yang, Zhou; Jin, Sunghwan; Wang, Bin; Park, Hyo Ju; Li, Yunqing; Qu, Deshun; Kwon, Youngwoo; Chen, Xianjue; Lee, Sun Hwa; Willinger, Marc Georg; Yoo, Won Jong; Lee, Zonghoon; Ruoff, Rodney S.

doi:10.1038/s41565-019-0622-8

Cited by 170 publications

(174 citation statements)

References 48 publications

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“…These include: 1) the high ratio of hydrogen/methane to terminate the graphene edges with hydrogen atom. The detachment of graphene edges from growth substrate promotes the diffusion of active carbon species into the interface for the formation of bilayer graphene with a yield of 99%; [ 82 ] 2) the designs of high Ni concentration (23%) in Cu−Ni alloy and long growth time for the isothermal growth of bilayer graphene with a yield of 99.4%; [ 83 ] 3) the use of large‐area single‐crystal Cu/Ni(111) alloy with Ni concentration of 16.6% for the formation of bilayer graphene with a yield of almost 100%; [ 84 ] 4) the introduction of ultra‐low‐limit methane concentration (0.01, 0.03, 0.06, and 0.1%) on Cu–Si alloy to produce a SiC layer, achieving the control of graphene layer number from mono‐, bi‐, tri‐, and tetralayer graphene after the sublimation of Si atoms, respectively. [ 85 ] Drawing on these strategies, the uniform tBLG was expected to be formed.…”

Section: The Manufacturing Techniques Of Tblgmentioning

confidence: 99%

Fabrication Strategies of Twisted Bilayer Graphenes and Their Unique Properties

Cai

2021

Advanced Materials

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Therefore, graphene becomes a rising star on the horizon of materials science. Since the first report of centimeter-scale single-crystal graphene by Ruoff group showed high electrical quality, [9] great achievements have been made in the fabrication of high-quality graphene for the application in electronic devices, including single-crystalline graphene flakes, [10,11] super-ordered graphene structures, [12,13] super-clean graphene films, [14-16] and ultra-flat graphene films. [17] However, the zero-bandgap feature for monolayer graphene has limited its potential applications in semiconductors. In addition, the negligible mass, low yield, and high production costs of graphene are insurmountable bottlenecks for the practical application in energy conversion and storage. In particular, the absence of killer applications leads to the increased difficulty in graphene commercialization. [18,19] Nevertheless, it is undeniable that the unique structure of graphene has sparked intense interest in condensed matter physics, such as fractional quantum Hall effects, [17] proton permeation, [20] and plasmons. [21] More interestingly, twisted bilayer graphene (tBLG), which is similar to the van der Waals heterostructures, has a dramatic effect on the electronic properties. [22,23] The relative rotating graphene layers become a powerful model to study topological physical properties, including ferromagnetism, [24] Mott insulating behavior and superconducting behaviors, [25,26] topological valley transport, [27] van Hove singularities, [28] and tunable bandgap. [29] Consequently, the twisted structure of tBLG has triggered tremendous enthusiasm, even inspiring the formation of a new field for twisted 2D materials. Currently, production methods of tBLG contain chemical vapor deposition (CVD) on metal catalysts; [30] epitaxial growth on SiC substrate; [31] folding monolayer graphene, [32] and stacking monolayer graphene. [33] These methods are divided into two categories: direct growth and manual assembly. Generally, the direct growth of tBLG undergoes an in situ rearrangement of carbon atoms in the non-equilibrium state at high temperatures, whereas the ex situ vertical overlap of monolayer graphene by transfer process is the basic principle for manual assembly. The completely different preparation processes give rise to the distinctive advantages and disadvantages, but precise control over twist angle and super-clean interface are the ultimate pursuits for any preparation method. Recent progress in Twisted bilayer graphene (tBLG) exhibits a host of innovative physical phenomena owing to the formation of moiré superlattice. Especially, the discovery of superconducting behavior has generated new interest in graphene. The growing studies of tBLG mainly focus on its physical properties, while the fabrication of high-quality tBLG is a prerequisite for achieving the desired properties due to the great dependence on the twist angle and the interfacial contact. Here, the cutting-edge preparation strategies and challenges of tBLG fabrica...

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Section: The Manufacturing Techniques Of Tblgmentioning

confidence: 99%

Fabrication Strategies of Twisted Bilayer Graphenes and Their Unique Properties

Cai

2021

Advanced Materials

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“…The advantages and disadvantages of this single-nucleus strategy for single-crystal BLG growth are similar to those of SLG grown from a single nucleus, that is, it is not necessary to use a single-crystal substrate, but the growth rate is usually very low. And, if using single crystal Cu/Ni(111) alloy as the substrates, single crystal multilayer graphene islands with three to eight layers and sizes of more than 150 μm have been reported [91].…”

Section: Synthesis Of Single-crystal Blgmentioning

confidence: 99%

Synthesis of Large-Area Single-Crystal Graphene

Wang

Luo

Wang

et al. 2021

Trends in Chemistry

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There have been breakthroughs in the mass production of graphene by chemical vapor deposition (CVD) and its practical applications have also been identified. Grain boundaries are typically present in 'CVD graphene' and adversely impact its properties. We summarize recent progress in growing large-area singlecrystal graphene. Centimeter-scale single-crystal, truly single-layer graphene (SLG) films have been reportedly achieved on single-crystal Cu(111) foils by CVD growth, while meter-scale single-crystal SLG films have been reportedly produced with assistance of a roll-to-roll technique. The growth of uniform single crystals of bilayer or multilayer graphene over a large area remains an exciting challenge. Layer-by-layer transfer and the stacking of single-crystal SLG is considered a promising route to making new types of 'single' crystals or quasicrystals with specific numbers of layers and different stacking angles. Structure and Properties of Single-Crystal GrapheneGraphene, a single layer of carbon atoms arranged in a honeycomb lattice (Figure 1A), has attracted worldwide attention due to its unique 2D structure and excellent physical properties [1][2][3][4][5]. When two graphene layers are stacked on top of each other, the properties of the bilayer material [6] depend on the stacking angle (Figure 1B,C) [7,8]. AB-stacked bilayer graphene (BLG) (see Glossary) reportedly has a continuously tunable bandgap of up to 250 meV when a vertical electrical field is applied, which enables the fabrication of semiconductor devices [9][10][11]. An AB-stacked BLG film was reportedly converted to an ultra-thin 'diamond' film (F-diamane) by fluorine chemisorption [12]. In addition, twisted bilayer graphene (tBLG) reportedly presents θ-dependent interfacial conductivity [13], van Hove singularities [14], and particular electronic structures [15] that are reported to have potential for use in ultra-sensitive sensors and ultra-thin capacitors. A Mott insulator and unconventional superconductivity with a critical temperature up to 1.7 K was reported for a twist angle of 1.1 o in BLG [10,11]. Compared with AB-stacked BLG, tBLG reportedly has a higher chemical reactivity, which was said to be due to distinct variations in the density-of-states distribution in the gap region [16]. Among various synthesis methods, chemical vapor deposition (CVD) has shown to be the most promising for the scalable production of large-area high-quality graphene films [17]. Ruoff and colleagues first reported the preparation of a centimeter-scale single-layer graphene (SLG) film on a commercial Cu foil by CVD in 2009 [18]. Unlike Ni with high carbon solubility (~0.9 at.% at 900°C [19]), Cu has a much lower carbon solubility, even up to 1000°C (7.4 at. ppm at 1020°C [20]), which is believed to predominantly contribute to the surface-mediated mechanism of graphene growth and good uniformity of the number of layers of the as-grown graphene [21]. As a result, Cu-based foils or films are the most common substrates for studying the behavior of graphene growt...

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“…For example, it has been widely acknowledged that certain kinds of alloy based on Cu provides special merits that allow the precise control of the layer number and domain size, and realize fast growth. [55][56][57] Compared to the Cu substrate, the alloy can be relatively more inexpensive, while further promoting the development of fabrication techniques. The best substrate would be comprehensively determined by the quality and performance of the derived 2D materials, as well as their processability and cost.…”

Section: Perspectives and Prospectsmentioning

confidence: 99%

Recent Advances in Growth of Large‐Sized 2D Single Crystals on Cu Substrates

Fan

Liu

et al. 2020

Advanced Materials

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benefits over other approaches, including mechanical exfoliation, epitaxial growth on SiC substrate, reduction of graphene oxides and molecular self-assembly. It has been widely recognized that the approach for scaled fabrication of 2D materials should have advantages both on quantities and quality for further advanced industrial uses. [8-10] In brief, CVD can make largescale and high-quality of 2D materials on a metal substrate at high temperature. The key point of the CVD approach lies in that it can realize fine control over nucleation and growth stages of 2D materials by purposely modulating CVD growth parameters. Currently, the reported size of single-crystal 2D materials has been reached up to meterscale, [11] paving the way toward industrial production and scaled applications. In the whole CVD growth process for 2D materials, there usually exist several para meters that can largely affect the final growth of materials, such as temperature, pressure, gas flow rate, catalyst and growth time and so on. Of all those parameters, the catalysts have been considered as the most important one for fabrication of large-sized and high-quality 2D materials. [12-14] Two reasons are recognized to support the viewpoint, both of which are highly related to the nucleation and growth stages of 2D crystals. Graphene growth on surface of catalysts is taken as an example. Large-scale and high-quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large-sized and singlecrystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large-sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h-BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in-depth growth dynamics and kinetics. Finally, relevant issues for industrialscale mass production of 2D single crystals are discussed and a promising future is expected.

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Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil

Cited by 170 publications

References 48 publications

Fabrication Strategies of Twisted Bilayer Graphenes and Their Unique Properties

Fabrication Strategies of Twisted Bilayer Graphenes and Their Unique Properties

Synthesis of Large-Area Single-Crystal Graphene

Recent Advances in Growth of Large‐Sized 2D Single Crystals on Cu Substrates

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