High Moisture-Barrier Performance of Double-Layer Graphene Enabled by Conformal and Clean Transfer.

Graphene films that can theoretically block almost all molecules have emerged as promising candidate materials for moisture barrier films in the applications of organic photonic devices and gas storage. However, the current barrier performance of graphene films does not reach the ideal value. Here, we reveal that the interlayer distance of the large-area stacked multilayer graphene is the key factor that suppresses water permeation. We show that by minimizing the gap between the two monolayers, the water vapor transmission rate of double-layer graphene can be as low as 5 × 10-3 g/(m2 d) over an A4-sized region. The high barrier performance was achieved by the absence of interfacial contamination and conformal contact between graphene layers during layer-by-layer transfer. Our work reveals the moisture permeation mechanism through graphene layers, and with this approach, we can tailor the interlayer coupling of manually stacked two-dimensional materials for new physics and applications.

Understanding Interlayer Contact Conductance in Twisted Bilayer Graphene.

Bilayer or few-layer 2D materials showing novel electrical properties in electronic device applications have aroused increasing interest in recent years. Obtaining a comprehensive understanding of interlayer contact conductance still remains a challenge, but is significant for improving the performance of bilayer or few-layer 2D electronic devices. Here, conductive atomic force microscope (C-AFM) experiments are reported to explore the interlayer contact conductance between bilayer graphene (BLG) with various twisted stacking structures fabricated by the chemical vapor deposition (CVD) method. The current maps show that the interlayer contact conductance between BLG strongly depends on the twist angle. The interlayer contact conductance of 0° AB-stacking bilayer graphene (AB-BLG) is ≈4 times as large as that of 30° twisted bilayer graphene (t-BLG), which indicates that the twist angle-dependent interlayer contact conductance originates from the coupling-decoupling transitions. Moreover, the moiré superlattice-level current images of t-BLG show modulations of local interlayer contact conductance. Density functional theory calculations together with a theoretical model reproduce the C-AFM current map and show that the modulation is mainly attributed to the overall contribution of local interfacial carrier density and tunneling barrier.

Superclean Growth of Graphene Using a Cold-Wall Chemical Vapor Deposition Approach.

Chemical vapor deposition (CVD) has become a promising approach for the industrial production of graphene films with appealing controllability and uniformity. However, in the conventional hot-wall CVD system, CVD-derived graphene films suffer from surface contamination originating from the gas-phase reaction during the high-temperature growth. Shown here is that the cold-wall CVD system is capable of suppressing the gas-phase reaction, and achieves the superclean growth of graphene films in a controllable manner. The as-received superclean graphene film, exhibiting improved optical and electrical properties, was proven to be an ideal candidate material used as transparent electrodes and substrate for epitaxial growth. This study provides a new promising choice for industrial production of high-quality graphene films, and the finding about the engineering of the gas-phase reaction, which is usually overlooked, will be instructive for future research on CVD growth of graphene.

Copper-Containing Carbon Feedstock for Growing Superclean Graphene.

Chemical vapor deposition (CVD) enables the large-scale growth of high-quality graphene film and exhibits considerable potential for the industrial production of graphene. However, CVD-grown graphene film contains surface contamination, which in turn hinders its potential applications, for example, in electrical and optoelectronic devices and in graphene-membrane-based applications. To solve this issue, we demonstrated a modified gas-phase reaction to achieve the large-scale growth of contamination-free graphene film, i.e., superclean graphene, using a metal-containing molecule, copper(II) acetate, Cu(OAc)2, as the carbon source. During high-temperature CVD, the Cu-containing carbon source significantly increased the Cu content in the gas phase, which in turn suppressed the formation of contamination on the graphene surface by ensuring sufficient decomposition of the carbon feedstock. The as-received graphene with a surface cleanness of about 99% showed enhanced optical and electrical properties. This study opens a new avenue for improving graphene quality with respect to surface cleanness and provides new insight into the mechanism of graphene growth through the gas-phase reaction pathway.

Large-Area Synthesis of Superclean Graphene via Selective Etching of Amorphous Carbon with Carbon Dioxide.

Contamination commonly observed on the graphene surface is detrimental to its excellent properties and strongly hinders its application. It is still a great challenge to produce large-area clean graphene film in a low-cost manner. Herein, we demonstrate a facile and scalable chemical vapor deposition approach to synthesize meter-sized samples of superclean graphene with an average cleanness of 99 %, relying on the weak oxidizing ability of CO2 to etch away the intrinsic contamination, i.e., amorphous carbon. Remarkably, the elimination of amorphous carbon enables a significant reduction of polymer residues in the transfer of graphene films and the fabrication of graphene-based devices and promises strongly enhanced electrical and optical properties of graphene. The facile synthesis of large-area superclean graphene would open the pathway for both fundamental research and industrial applications of graphene, where a clean surface is highly needed.

Low-Temperature and Rapid Growth of Large Single-Crystalline Graphene with Ethane.

Future applications of graphene rely highly on the production of large-area high-quality graphene, especially large single-crystalline graphene, due to the reduction of defects caused by grain boundaries. However, current large single-crystalline graphene growing methodologies are suffering from low growth rate and as a result, industrial graphene production is always confronted by high energy consumption, which is primarily caused by high growth temperature and long growth time. Herein, a new growth condition achieved via ethane being the carbon feedstock to achieve low-temperature yet rapid growth of large single-crystalline graphene is reported. Ethane condition gives a growth rate about four times faster than methane, achieving about 420 µm min-1 for the growth of sub-centimeter graphene single crystals at temperature about 1000 °C. In addition, the temperature threshold to obtain graphene using ethane can be reduced to 750 °C, lower than the general growth temperature threshold (about 1000 °C) with methane on copper foil. Meanwhile ethane always keeps higher graphene growth rate than methane under the same growth temperature. This study demonstrates that ethane is indeed a potential carbon source for efficient growth of large single-crystalline graphene, thus paves the way for graphene in high-end electronical and optoelectronical applications.

Two-Dimensional (C4H9NH3)2PbBr4 Perovskite Crystals for High-Performance Photodetector.

Two-dimensional (2D) layered hybrid perovskites of (RNH3)2PbX4 (R is an alkyl and X is a halide) have been recently synthesized and exhibited rich optical properties including fluorescence and exciton effects. However, few studies on transport and optoelectronic measurements of individual 2D perovskite crystals have been reported, presumably owing to the instability issue during electronic device fabrications. Here we report the first photodetector based on individual 2D (C4H9NH3)2PbBr4 perovskite crystals, built with the protection and top contact of graphene film. Both a high responsivity (∼2100 A/W) and extremely low dark current (∼10-10 A) are achieved with a design of interdigital graphene electrodes. Our study paves the way to build high-performance optoelectronic devices based on the emerging 2D single-crystal perovskite materials.

Super Graphene-Skinned Materials: An Innovative Strategy toward Graphene Applications.

Super graphene-skinned materials are emerging members of the graphene composite materials family, which are produced through the high-temperature chemical deposition of continuous graphene layers on traditional engineering materials. The high-performance graphene "skin" endows the traditional engineering materials with additional functionalities, and atomically thin graphene films enter the market by hitching a ride on traditional material carriers. Beyond the physical coating of graphene powders onto engineering materials, the directly grown continuous graphene skin keeps its excellent intrinsic properties to a great extent and holds promise for future applications. Super graphene-skinned material is an innovative pathway for applications of continuous graphene films, which avoids the challenging peeling-transfer process and solves the non-self-supporting issue of ultrathin graphene film. It is a big family, including graphene-skinned powders, fibers, foils, and foams. With further processing and molding, we can obtain graphene-dispersed bulk materials, especially for metal-based graphene-skinned materials, which provides a creative pathway for uniformly dispersing graphene into a metal matrix. In practical applications, graphene-skinned materials would exhibit excellent performance with perfect processing compatibility with current engineering materials and be pushed to real industrial applications relying on the broad market of engineering materials.

Oxidization-Temperature-Triggered Rapid Preparation of Large-Area Single-Crystal Cu(111) Foil.

The controlled preparation of single-crystal Cu(111) is intensively investigated owing to the superior properties of Cu(111) and its advantages in synthesizing high-quality 2D materials, especially graphene. However, the accessibility of large-area single-crystal Cu(111) is still hindered by time-consuming, complicated, and high-cost preparation methods. Here, the oxidization-temperature-triggered rapid preparation of large-area single-crystal Cu(111) in which an area up to 320 cm2 is prepared within 60 min, and where low-temperature oxidization of polycrystalline Cu foil surface plays a vital role, is reported. A mechanism is proposed, by which the thin Cux O layer transforms to a Cu(111) seed layer on the surface of Cu to induce the formation of a large-area Cu(111) foil, which is supported by both experimental data and molecular dynamics simulation results. In addition, a large-size high-quality graphene film is synthesized on the single-crystal Cu(111) foil surface and the graphene/Cu(111) composites exhibit enhanced thermal conductivity and ductility compared to their polycrystalline counterpart. This work, therefore, not only provides a new avenue toward the monocrystallinity of Cu with specific planes but also contributes to improving the mass production of high-quality 2D materials.

Rationalized Electroepitaxy toward Scalable Single-Crystal Zn Anodes.

Electroepitaxy is recognized as an effective approach to prepare metal electrodes with nearly complete reversibility. Nevertheless, large-scale manipulation is still not attainable owing to complicated interfacial chemistry. Here, the feasibility of extending Zn electroepitaxy toward the bulk phase over a mass-produced mono-oriented Cu(111) foil is demonstrated. Interfacial Cu-Zn alloy and turbulent electroosmosis are circumvented by adopting a potentiostatic electrodeposition protocol. The as-prepared Zn single-crystalline anode enables stable cycling of symmetric cells at a stringent current density of 50.0 mA cm-2 . The assembled full cell further sustaines a capacity retention of 95.7% at 5.0 A g-1 for 1500 cycles, accompanied by a controllably low N/P ratio of 7.5. In addition to Zn, Ni electroepitaxy can be realized by using the same approach. This study may inspire rational exploration of the design of high-end metal electrodes.

Fast synthesis of large-area bilayer graphene film on Cu.

Bilayer graphene (BLG) is intriguing for its unique properties and potential applications in electronics, photonics, and mechanics. However, the chemical vapor deposition synthesis of large-area high-quality bilayer graphene on Cu is suffering from a low growth rate and limited bilayer coverage. Herein, we demonstrate the fast synthesis of meter-sized bilayer graphene film on commercial polycrystalline Cu foils by introducing trace CO2 during high-temperature growth. Continuous bilayer graphene with a high ratio of AB-stacking structure can be obtained within 20 min, which exhibits enhanced mechanical strength, uniform transmittance, and low sheet resistance in large area. Moreover, 96 and 100% AB-stacking structures were achieved in bilayer graphene grown on single-crystal Cu(111) foil and ultraflat single-crystal Cu(111)/sapphire substrates, respectively. The AB-stacking bilayer graphene exhibits tunable bandgap and performs well in photodetection. This work provides important insights into the growth mechanism and the mass production of large-area high-quality BLG on Cu.

Slip-Line-Guided Growth of Graphene.

Manipulating the crystal orientation of emerging 2D materials via chemical vapor deposition (CVD) is a key premise for obtaining single-crystalline films and designing specific grain-boundary (GB) structures. Herein, the controllable crystal orientation of graphene during the CVD process is demonstrated on a single-crystal metal surface with preexisting atomic-scale stair steps resulting from dislocation slip lines. The slip-line-guided growth principle is established to explain and predict the crystal orientation distribution of graphene on a variety of metal facets, especially for the multidirectional growth cases on Cu(hk0) and Cu(hkl) substrates. Not only large-area single-crystal graphene, but also bicrystal graphene with controllable GB misorientations, are successfully synthesized by rationally employing tailored metal substrate facets. As a demonstration, bicrystal graphenes with misorientations of ≈21° and ≈11° are constructed on Cu(410) and Cu(430) foils, respectively. This guideline builds a bridge linking the crystal orientation of graphene and the substrate facet, thereby opening a new avenue for constructing bicrystals with the desired GB structures or manipulating 2D superlattice twist angles in a bottom-up manner.

Toward Epitaxial Growth of Misorientation-Free Graphene on Cu(111) Foils.

The epitaxial growth of single-crystal thin films relies on the availability of a single-crystal substrate and a strong interaction between epilayer and substrate. Previous studies have reported the roles of the substrate (e.g., symmetry and lattice constant) in determining the orientations of chemical vapor deposition (CVD)-grown graphene, and Cu(111) is considered as the most promising substrate for epitaxial growth of graphene single crystals. However, the roles of gas-phase reactants and graphene-substrate interaction in determining the graphene orientation are still unclear. Here, we find that trace amounts of oxygen is capable of enhancing the interaction between graphene edges and Cu(111) substrate and, therefore, eliminating the misoriented graphene domains in the nucleation stage. A modified anomalous grain growth method is developed to improve the size of the as-obtained Cu(111) single crystal, relying on strongly textured polycrystalline Cu foils. The batch-to-batch production of A3-size (∼0.42 × 0.3 m2) single-crystal graphene films is achieved on Cu(111) foils relying on a self-designed pilot-scale CVD system. The as-grown graphene exhibits ultrahigh carrier mobilities of 68 000 cm2 V-1 s-1 at room temperature and 210 000 cm2 V-1 s-1 at 2.2 K. The findings and strategies provided in our work would accelerate the mass production of high-quality misorientation-free graphene films.

Transfer-Enabled Fabrication of Graphene Wrinkle Arrays for Epitaxial Growth of AlN Films.

Formation of graphene wrinkle arrays can periodically alter the electrical properties and chemical reactivity of graphene, which is promising for numerous applications. However, large-area fabrication of graphene wrinkle arrays remains unachievable with a high density and defined orientations, especially on rigid substrates. Herein, relying on the understanding of the formation mechanism of transfer-related graphene wrinkles, the graphene wrinkle arrays are fabricated without altering the crystalline orientation of entire graphene films. The choice of the transfer medium that has poor wettability on the corrugated surface of graphene is proven to be the key for the formation of wrinkles. This work provides a deep understanding of formation process of transfer-related graphene wrinkles and opens up a new way for periodically modifying the surface properties of graphene for potential applications, including direct growth of AlN epilayers and deep ultraviolet light emitting diodes.

Integrated wafer-scale ultra-flat graphene by gradient surface energy modulation.

The integration of large-scale two-dimensional (2D) materials onto semiconductor wafers is highly desirable for advanced electronic devices, but challenges such as transfer-related crack, contamination, wrinkle and doping remain. Here, we developed a generic method by gradient surface energy modulation, leading to a reliable adhesion and release of graphene onto target wafers. The as-obtained wafer-scale graphene exhibited a damage-free, clean, and ultra-flat surface with negligible doping, resulting in uniform sheet resistance with only ~6% deviation. The as-transferred graphene on SiO2/Si exhibited high carrier mobility reaching up ~10,000 cm2 V-1 s-1, with quantum Hall effect (QHE) observed at room temperature. Fractional quantum Hall effect (FQHE) appeared at 1.7 K after encapsulation by h-BN, yielding ultra-high mobility of ~280,000 cm2 V-1 s-1. Integrated wafer-scale graphene thermal emitters exhibited significant broadband emission in near-infrared (NIR) spectrum. Overall, the proposed methodology is promising for future integration of wafer-scale 2D materials in advanced electronics and optoelectronics.

Large-area transfer of two-dimensional materials free of cracks, contamination and wrinkles via controllable conformal contact.

The availability of graphene and other two-dimensional (2D) materials on a wide range of substrates forms the basis for large-area applications, such as graphene integration with silicon-based technologies, which requires graphene on silicon with outperforming carrier mobilities. However, 2D materials were only produced on limited archetypal substrates by chemical vapor deposition approaches. Reliable after-growth transfer techniques, that do not produce cracks, contamination, and wrinkles, are critical for layering 2D materials onto arbitrary substrates. Here we show that, by incorporating oxhydryl groups-containing volatile molecules, the supporting films can be deformed under heat to achieve a controllable conformal contact, enabling the large-area transfer of 2D films without cracks, contamination, and wrinkles. The resulting conformity with enhanced adhesion facilitates the direct delamination of supporting films from graphene, providing ultraclean surfaces and carrier mobilities up to 1,420,000 cm2 V-1 s-1 at 4 K.

Decimeter-Scale Atomically Thin Graphene Membranes for Gas-Liquid Separation.

Graphene holds great potential for fabricating ultrathin selective membranes possessing high permeability without compromising selectivity and has attracted intensive interest in developing high-performance separation membranes for desalination, natural gas purification, hemodialysis, distillation, and other gas-liquid separation. However, the scalable and cost-effective synthesis of nanoporous graphene membranes, especially designing a method to produce an appropriate porous polymer substrate, remains very challenging. Here, we report a facile route to fabricate decimeter-scale (∼15 × 10 cm2) nanoporous atomically thin membranes (NATMs) via the direct casting of the porous polymer substrate onto graphene, which was produced by chemical vapor deposition (CVD). After the vapor-induced phase-inversion process under proper experimental conditions (60 °C and 60% humidity), the flexible nanoporous polymer substrate was formed. The resultant skin-free polymer substrate, which had the proper pore size and a uniform spongelike structure, provided enough mechanical support without reducing the permeance of the NATMs. It was demonstrated that after creating nanopores by the O2 plasma treatment, the NATMs were salt-resistant and simultaneously showed 3-5 times higher gas (CO2) permeance than the state-of-the-art commercial polymeric membranes. Therefore, our work provides guidance for the technological developments of graphene-based membranes and bridges the gap between the laboratory-scale "proof-of-concept" and the practical applications of NATMs in the industry.

Tunable Pore Size from Sub-Nanometer to a Few Nanometers in Large-Area Graphene Nanoporous Atomically Thin Membranes.

Membranes are key components in chemical purification, biological separation, and water desalination. Traditional polymeric membranes are subjected to a ubiquitous trade-off between permeance and selectivity, which significantly hinders the separation performance. Nanoporous atomically thin membranes (NATMs), such as graphene NATMs, have the potential to break this trade-off. Owing to their uniqueness of two-dimensional structure and potential nanopore structure controllability, NATMs are expected to have outstanding selectivity through molecular sieving while achieving ultimate permeance at the same time. However, a drastic selectivity discrepancy exists between the proof-of-concept demonstrations and scalable separation applications in graphene membranes. In this paper, we offer a possible solution to narrow this discrepancy by tuning the pore density and pore size separately with two successive plasma treatments. We demonstrate that by narrowing the pore size distribution, the selectivity of graphene membranes can be greatly increased. Low-energy argon plasma is first applied to nucleate high density of defects in graphene. Controlled oxygen plasma is then utilized to selectively enlarge the defects into nanopores with desired sizes. This method is scalable, and the fabricated 1 cm2 graphene NATMs with sub-nanometer pores can separate KCl and Allura Red with a selectivity of 104 and a permeance of 1.1 × 10-6 m s-1. The pores in NATMs can be further tuned from gas-selective sub-nanometer pores to a few nanometer size. The fabricated NATMs show a selectivity of 35 between CO2 and N2. With longer enlargement time, a selectivity of 21.2 between a lysozyme and bovine serum albumin can also be achieved with roughly four times higher permeance than that of a commercial dialysis membrane. This research offers a solution to realize NATMs of tunable pore size with a narrow pore size distribution for different separation processes from sub-nanometer in gas separation or desalination to a few nanometers in dialysis.

Hetero-site nucleation for growing twisted bilayer graphene with a wide range of twist angles.

Twisted bilayer graphene (tBLG) has recently attracted growing interest due to its unique twist-angle-dependent electronic properties. The preparation of high-quality large-area bilayer graphene with rich rotation angles would be important for the investigation of angle-dependent physics and applications, which, however, is still challenging. Here, we demonstrate a chemical vapor deposition (CVD) approach for growing high-quality tBLG using a hetero-site nucleation strategy, which enables the nucleation of the second layer at a different site from that of the first layer. The fraction of tBLGs in bilayer graphene domains with twist angles ranging from 0° to 30° was found to be improved to 88%, which is significantly higher than those reported previously. The hetero-site nucleation behavior was carefully investigated using an isotope-labeling technique. Furthermore, the clear Moiré patterns and ultrahigh room-temperature carrier mobility of 68,000 cm2 V-1 s-1 confirmed the high crystalline quality of our tBLG. Our study opens an avenue for the controllable growth of tBLGs for both fundamental research and practical applications.

Controlled Growth of Single-Crystal Graphene Films.

Grain boundaries produced during material synthesis affect both the intrinsic properties of materials and their potential for high-end applications. This effect is commonly observed in graphene film grown using chemical vapor deposition and therefore caused intense interest in controlled growth of grain-boundary-free graphene single crystals in the past ten years. The main methods for enlarging graphene domain size and reducing graphene grain boundary density are classified into single-seed and multiseed approaches, wherein reduction of nucleation density and alignment of nucleation orientation are respectively realized in the nucleation stage. On this basis, detailed synthesis strategies, corresponding mechanisms, and key parameters in the representative methods of these two approaches are separately reviewed, with the aim of providing comprehensive knowledge and a snapshot of the latest status of controlled growth of single-crystal graphene films. Finally, perspectives on opportunities and challenges in synthesizing large-area single-crystal graphene films are discussed.