Epitaxial Growth of 6 in. Single‐Crystalline Graphene on a Cu/Ni (111) Film at 750 °C via Chemical Vapor Deposition

The future electronic application of graphene highly relies on the production of large‐area high‐quality single‐crystal graphene. However, the growth of single‐crystal graphene on different substrates via either single nucleation or seamless stitching is carried out at a temperature of 1000 °C or higher. The usage of this high temperature generates a variety of problems, including complexity of operation, higher contamination, metal evaporation, and wrinkles owing to the mismatch of thermal expansion coefficients between the substrate and graphene. Here, a new approach for the fabrication of ultraflat single‐crystal graphene using Cu/Ni (111)/sapphire wafers at lower temperature is reported. It is found that the temperature of epitaxial growth of graphene using Cu/Ni (111) can be reduced to 750 °C, much lower than that of earlier reports on catalytic surfaces. Devices made of graphene grown at 750 °C have a carrier mobility up to ≈9700 cm² V^?1 s^?1 at room temperature. This work shines light on a way toward a much lower temperature growth of high‐quality graphene in single crystallinity, which could benefit future electronic applications.     

Synthesis of Large‐Area InSe Monolayers by Chemical Vapor Deposition

Recently, 2D materials of indium selenide (InSe) layers have attracted much attention from the scientific community due to their high mobility transport and fascinating physical properties. To date, reports on the synthesis of high‐quality and scalable InSe atomic films are limited. Here, a synthesis of InSe atomic layers by vapor phase selenization of In₂O₃ in a chemical vapor deposition (CVD) system, resulting in large‐area monolayer flakes or thin films, is reported. The atomic films are continuous and uniform over a large area of 1 × 1 cm², comprising of primarily InSe monolayers. Spectroscopic and microscopic measurements reveal the highly crystalline nature of the synthesized InSe monolayers. The ion‐gel‐gated field‐effect transistors based on CVD InSe monolayers exhibit n‐type channel behaviors, where the field effect electron mobility values can be up to ≈30 cm² V^?1 s^?1 along with an on/off current ratio, of >10⁴ at room temperature. In addition, the graphene can serve as a protection layer to prevent the oxidation between InSe and the ambient environment. Meanwhile, the synthesized InSe films can be transferred to arbitrary substrates, enabling the possibility of reassembly of various 2D materials into vertically stacked heterostructures, prompting research efforts to probe its characteristics and applications.     

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High‐Mobility MoS2 Field‐Effect Transistors

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post‐silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high‐performance devices while adapting for large‐area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS₂ devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD‐grown MoS₂ film and a Ag electrode as an interfacial layer. The MoS₂ field‐effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field‐effect mobility of 35 cm² V^?1 s^?1, an on/off current ratio of 4 × 10⁸, and a photoresponsivity of 2160 A W^?1, compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n‐doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS₂ and electrodes. This demonstration of contact interface engineering with CVD‐grown MoS₂ and graphene is a key step toward the practical application of atomically thin TMDC‐based devices with low‐resistance contacts for high‐performance large‐area electronics and optoelectronics.     

Copper‐Vapor‐Assisted Growth and Defect‐Healing of Graphene on Copper Surfaces

Although there is significant progress in the chemical vapor deposition (CVD) of graphene on Cu surfaces, the industrial application of graphene is not realized yet. One of the most critical obstacles that limit the commercialization of graphene is that CVD graphene contains too many vacancies or sp³‐type defects. Therefore, further investigation of the growth mechanism is still required to control the defects of graphene. During the growth of graphene, sublimation of the Cu catalyst to produce Cu vapor occurs inevitably because the process temperature is close to the melting point of Cu. However, to date few studies have investigated the effects of Cu vapor on graphene growth. In this study, how the Cu vapor produced by sublimation affects the chemical vapor deposition of graphene on Cu surfaces is investigated. It is found that the presence of Cu vapor enlarges the graphene grains and enhances the efficiency of the defect‐healing of graphene by CH₄. It is elucidated that these effects are due to the removal by Cu vapor of carbon adatoms from the Cu surface and oxygen‐functionalized carbons from graphene. Finally, these insights are used to develop a method for the synthesis of uniform and high‐quality graphene.     

Toward Mass Production of CVD Graphene Films

Chemical vapor deposition (CVD) is considered to be an efficient method for fabricating large‐area and high‐quality graphene films due to its excellent controllability and scalability. Great efforts have been made to control the growth of graphene to achieve large domain sizes, uniform layers, fast growth, and low synthesis temperatures. Some attempts have been made by both the scientific community and startup companies to mass produce graphene films; however, there is a large difference in the quality of graphene synthesized on a laboratory scale and an industrial scale. Here, recent progress toward the mass production of CVD graphene films is summarized, including the manufacturing process, equipment, and critical process parameters. Moreover, the large‐scale homogeneity of graphene films and fast characterization methods are also discussed, which are crucial for quality control in mass production.     

3D Graphene Fibers Grown by Thermal Chemical Vapor Deposition

3D assembly of graphene sheets (GSs) is important for preserving the merits of the single‐atomic‐layered structure. Simultaneously, vertical growth of GSs has long been a challenge for thermal chemical vapor deposition (CVD). Here, vertical growth of the GSs is achieved in a thermal CVD reactor and a novel 3D graphene structure, 3D graphene fibers (3DGFs), is developed. The 3DGFs are prepared by carbonizing electrospun polyacrylonitrile fibers in NH₃ and subsequently in situ growing the radially oriented GSs using thermal CVD. The GSs on the 3DGFs are densely arranged and interconnected with the edges fully exposed on the surface, resulting in high performances in multiple aspects such as electrical conductivity (3.4 × 10⁴–1.2 × 10⁵ S m^?1), electromagnetic shielding (60 932 dB cm² g^?1), and superhydrophobicity and superoleophilicity, which are far superior to the existing 3D graphene materials. With the extraordinary properties along with the easy scalability of the simple thermal CVD, the novel 3DGFs are highly promising for many applications such as high‐strength and conducting composites, flexible conductors, electromagnetic shielding, energy storage, catalysis, and separation and purification. Furthermore, this strategy can be widely used to grow the vertical GSs on many other substrates by thermal CVD.     

Achieving High Capacitance of Paper‐Like Graphene Films by Adsorbing Molecules from Hydrolyzed Polyimide

To date, graphene‐based electric double layer supercapacitors have not shown the remarkable specific capacitance as theoretically predicted. An efficient strategy toward boosting the overall capacitance is to endow graphene with pseudocapacitance. Herein, molecules of hydrolyzed polyimide (HPI) are used to functionalize N‐doped graphene (NG) via π–π interaction and the resulting enhanced electrochemical energy storage is reported. These aromatic molecules in monolayer form on graphene contribute strong pseudocapacitance. Paper‐like NG films with different areal mass loadings ranging from 0.5 to 4.8 mg cm^?2 are prepared for supercapacitor electrodes. It is shown that the gravimetric capacitance can be increased by 50–60% after the surface functionalization by HPI molecules. A high specific capacitance of 553 F g^?1 at 5 mV s^?1 is achieved by the HPI‐NG film with a graphene mass loading of 0.5 mg cm^?2 in H₂SO₄ aqueous electrolyte. For the HPI‐NG film with highest mass loading, the gravimetric specific capacitance drops to 340 F g^?1 while the areal specific capacitance reaches a high value of 1.7 F cm^?2. HPI‐NG films are also tested in Li₂SO₄ aqueous electrolyte, over an extended voltage window of 1.6 V. High specific energy densities up to 40 Wh kg^?1 are achieved with the Li₂SO₄ electrolyte.     

Direct Laser Writing of Graphene Made from Chemical Vapor Deposition for Flexible,Integratable Micro‐Supercapacitors with Ultrahigh Power Output

High‐performance yet flexible micro‐supercapacitors (MSCs) hold great promise as miniaturized power sources for increasing demand of integrated electronic devices. Herein, this study demonstrates a scalable fabrication of multilayered graphene‐based MSCs (MG‐MSCs), by direct laser writing (DLW) of stacked graphene films made from industry‐scale chemical vapor deposition (CVD). Combining the dry transfer of multilayered CVD graphene films, DLW allows a highly efficient fabrication of large‐areal MSCs with exceptional flexibility, diverse planar geometry, and capability of customer‐designed integration. The MG‐MSCs exhibit simultaneously ultrahigh energy density of 23 mWh cm^?3 and power density of 1860 W cm^?3 in an ionogel electrolyte. Notably, such MG‐MSCs demonstrate an outstanding flexible alternating current line‐filtering performance in poly(vinyl alcohol) (PVA)/H₂SO₄ hydrogel electrolyte, indicated by a phase angle of ?76.2° at 120 Hz and a resistance–capacitance constant of 0.54 ms, due to the efficient ion transport coupled with the excellent electric conductance of the planar MG microelectrodes. MG–polyaniline (MG‐PANI) hybrid MSCs fabricated by DLW of MG‐PANI hybrid films show an optimized capacitance of 3.8 mF cm^?2 in PVA/H₂SO₄ hydrogel electrolyte; an integrated device comprising MG‐MSCs line filtering, MG‐PANI MSCs, and pressure/gas sensors is demonstrated.     

Control of thickness uniformity and grain size in graphene films for transparent conductive electrodes

Large-scale and transferable graphene films grown on metal substrates by chemical vapor deposition (CVD) still hold great promise for future nanotechnology. To realize the promise, one of the key issues is to further improve the quality of graphene, e.g., uniform thickness, large grain size, and low defects. Here we grow graphene films on Cu foils by CVD at ambient pressure, and study the graphene nucleation and growth processes under different concentrations of carbon precursor. On the basis of the results, we develop a two-step ambient pressure CVD process to synthesize continuous single-layer graphene films with large grain size (up to hundreds of square micrometers). Scanning electron microscopy and Raman spectroscopy characterizations confirm the film thickness and uniformity. The transferred graphene films on cover glass slips show high electrical conductivity and high optical transmittance that make them suitable as transparent conductive electrodes. The growth mechanism of CVD graphene on Cu is also discussed, and a growth model has been proposed. Our results provide important guidance toward the synthesis of high quality uniform graphene films, and could offer a great driving force for graphene based applications.     

High‐ versus Low‐Quality Graphene: A Mechanistic Investigation of Electrografted Diazonium‐Based Films for Growth of Polymer Brushes

Electrografting using aryldiazonium salts provides a fast and efficient technique to functionalize commercially available 3?5 layered graphene (vapour‐deposited) on nickel. In this study, Raman spectroscopy is used to quantify the grafting efficiency of cyclic voltammetry which is one of the most versatile, yet simple, electrochemical techniques available. To a large extent the number of defects/substituents introduced to the basal plane of high‐quality graphene by this procedure can be controlled through the sweeping conditions employed. After extended electrografting the defect density reaches a saturation level (～10¹³ cm^?2) which is independent of the quality of the graphene expressed through its initial content of defects. However, it is reached within fewer voltammetric cycles for low‐quality graphene. Based on these results it is suggested that the grafting occurs (a) directly at defect sites for, in particular, low‐quality graphene, (b) directly at the basal plane for, in particular, high‐quality graphene, and/or (c) at already grafted molecules to give a mushroom‐like film growth for all films. Moreover, it is shown that a tertiary alkyl bromide can be introduced at a given surface density to serve as radical initiator for surface‐initiated atom transfer radical polymerization (SI‐ATRP). Brushes of poly(methyl methacrylate) are grown from these substrates, and the relationship between polymer thickness and sweeping conditions is studied.     

High‐Mobility Helical Tellurium Field‐Effect Transistors Enabled by Transfer‐Free,Low‐Temperature Direct Growth

The transfer‐free direct growth of high‐performance materials and devices can enable transformative new technologies. Here, room‐temperature field‐effect hole mobilities as high as 707 cm² V^?1 s^?1 are reported, achieved using transfer‐free, low‐temperature (≤120 °C) direct growth of helical tellurium (Te) nanostructure devices on SiO₂/Si. The Te nanostructures exhibit significantly higher device performance than other low‐temperature grown semiconductors, and it is demonstrated that through careful control of the growth process, high‐performance Te can be grown on other technologically relevant substrates including flexible plastics like polyethylene terephthalate and graphene in addition to amorphous oxides like SiO₂/Si and HfO₂. The morphology of the Te films can be tailored by the growth temperature, and different carrier scattering mechanisms are identified for films with different morphologies. The transfer‐free direct growth of high‐mobility Te devices can enable major technological breakthroughs, as the low‐temperature growth and fabrication is compatible with the severe thermal budget constraints of emerging applications. For example, vertical integration of novel devices atop a silicon complementary metal oxide semiconductor platform (thermal budget <450 °C) has been theoretically shown to provide a 10× systems level performance improvement, while flexible and wearable electronics (thermal budget <200 °C) can revolutionize defense and medical applications.     

Transparent,High‐Thermal‐Conductivity Ultradrawn Polyethylene/Graphene Nanocomposite Films

Transparent, ultradrawn, ultrahigh molecular weight polyethylene (UHMWPE)/graphene nanocomposite films with a high thermal conductivity are successfully fabricated by solution‐casting and solid‐state drawing. It is found that the low optical transmittance (<75%) of the ultradrawn UHMWPE/graphene composite films is drastically improved (>90%) by adding 2‐(2H‐benzontriazol‐2‐yl)‐4,6‐ditertpentylphenol (BZT) as a second additive. This high transmission is interpreted in terms of a reduced void content in the composite films and the improved dispersion of graphene both of which decrease light scattering. The high thermal conductivity is attributed to the π–π interaction between BZT and graphene. In addition, a high specific thermal conductivity of ≈75 W m^?1 K^?1 ρ^?1 of the ultradrawn UHMWPE/graphene/BZT composite films is obtained, which is higher than most metals and polymer nanocomposite. These transparent films are potentially excellent candidates for thermal management in various applications due to a combination of low density, ease of processing, and high thermal conductivity.     

Wafer‐Scale Synthesis of Graphene on Sapphire: Toward Fab‐Compatible Graphene

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high‐quality material on technologically relevant substrates, over wafer‐scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal‐catalysts or yielding defective graphene. In this work, a metal‐free approach implemented in commercially available reactors to obtain high‐quality monolayer graphene on c‐plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al‐rich reconstruction $\left(\sqrt{31}\times \sqrt{31}\right)R\pm 9$° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high‐quality graphene with mobilities consistently above 2000 cm² V^?1 s^?1. The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back‐end‐of‐line integration. The growth process introduced here establishes a method for the synthesis of wafer‐scale graphene films on a technologically viable basis.     

Synthesis of isotopically-labeled graphite films by cold-wall chemical vapor deposition and electronic properties of graphene obtained from such films

We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition (CVD). During the synthesis, carbon from ¹²C- and ¹³C-methane was deposited on, and dissolved in, a nickel foil at high temperature, and a uniform graphite film was segregated from the nickel surface by cooling the sample to room temperature. Scanning and transmission electron microscopy, micro-Raman spectroscopy, and X-ray diffraction prove the presence of a graphite film. Monolayer graphene films obtained from such isotopically-labeled graphite films by mechanical methods have electron mobility values greater than 5000 cm²·V⁻¹·s⁻¹ at low temperatures. Furthermore, such films exhibit the half-integer quantum Hall effect over a wide temperature range from 2 K to 200 K, implying that the graphite grown by this cold-wall CVD approach has a quality as high as highly oriented pyrolytic graphite (HOPG). The results from transport measurements indicate that ¹³C-labeling does not significantly affect the electrical transport properties of graphene.     

Highly Conductive and Transparent Large‐Area Bilayer Graphene Realized by MoCl5 Intercalation

Bilayer graphene (BLG) comprises a 2D nanospace sandwiched by two parallel graphene sheets that can be used to intercalate molecules or ions for attaining novel functionalities. However, intercalation is mostly demonstrated with small, exfoliated graphene flakes. This study demonstrates intercalation of molybdenum chloride (MoCl₅) into a large‐area, uniform BLG sheet, which is grown by chemical vapor deposition (CVD). This study reveals that the degree of MoCl₅ intercalation strongly depends on the stacking order of the graphene; twist‐stacked graphene shows a much higher degree of intercalation than AB‐stacked. Density functional theory calculations suggest that weak interlayer coupling in the twist‐stacked graphene contributes to the effective intercalation. By selectively synthesizing twist‐rich BLG films through control of the CVD conditions, low sheet resistance (83 Ω ?^?1) is realized after MoCl₅ intercalation, while maintaining high optical transmittance (≈95%). The low sheet resistance state is relatively stable in air for more than three months. Furthermore, the intercalated BLG film is applied to organic solar cells, realizing a high power conversion efficiency.     

Direct evidence of advantage of Cu(111) for graphene synthesis by using Raman mapping and electron backscatter diffraction

The advantageous crystallographic orientation of Cu surface for graphene synthesis by using thermal chemical vapor deposition (CVD) is examined by Raman mapping and electron backscatter diffraction. It is found that Cu(111) predominates over (110) and (100) for single- (SLG) or few-layer graphene (FLG) growth. To confirm this result we attempt the synthesis of graphene on Cu(111) single crystal film surfaces. We confirmed the formation of high quality and high uniformity SLG or FLG over more than 97% of the substrate surface area of 10 mm × 10 mm by Raman mapping.     

Direct CVD Growth of Graphene on Traditional Glass: Methods and Mechanisms

Chemical vapor deposition (CVD) on catalytic metal surfaces is considered to be the most effective way to obtain large‐area, high‐quality graphene films. For practical applications, a transfer process from metal catalysts to target substrates (e.g., poly(ethylene terephthalate) (PET), glass, and SiO₂/Si) is unavoidable and severely degrades the quality of graphene. In particular, the direct growth of graphene on glass can avoid the tedious transfer process and endow traditional glass with prominent electrical and thermal conductivities. Such a combination of graphene and glass creates a new type of glass, the so‐called “super graphene glass,” which has attracted great interest from the viewpoints of both fundamental research and daily‐life applications. In the last few years, great progress has been achieved in pursuit of this goal. Here, these growth methods as well as the specific growth mechanisms of graphene on glass surfaces are summarized. The typical techniques developed include direct thermal CVD growth, molten‐bed CVD growth, metal‐catalyst‐assisted growth, and plasma‐enhanced growth. Emphasis is placed on the strategy of growth corresponding to the different natures of glass substrates. A comprehensive understanding of graphene growth on nonmetal glass substrates and the latest status of “super graphene glass” production are provided.     

N‐Doped Graphene Field‐Effect Transistors with Enhanced Electron Mobility and Air‐Stability

Although graphene can be easily p‐doped by various adsorbates, developing stable n‐doped graphene that is very useful for practical device applications is a difficult challenge. We investigated the doping effect of solution‐processed (4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)phenyl)dimethylamine (N‐DMBI) on chemical‐vapor‐deposited (CVD) graphene. Strong n‐type doping is confirmed by Raman spectroscopy and the electrical transport characteristics of graphene field‐effect transistors. The strong n‐type doping effect shifts the Dirac point to around ‐140 V. Appropriate annealing at a low temperature of 80 ºC enables an enhanced electron mobility of 1150 cm² V^?1 s^?1. The work function and its uniformity on a large scale (1.2 mm × 1.2 mm) of the doped surface are evaluated using ultraviolet photoelectron spectroscopy and Kelvin probe mapping. Stable electrical properties are observed in a device aged in air for more than one month.     

Low‐Temperature Heteroepitaxy of 2D PbI2/Graphene for Large‐Area Flexible Photodetectors

Heterostructures based on graphene and other 2D atomic crystals exhibit fascinating properties and intriguing potential in flexible optoelectronics, where graphene films function as transparent electrodes and other building blocks are used as photoactive materials. However, large‐scale production of such heterostructures with superior performance is still in early stages. Herein, for the first time, the preparation of a submeter‐sized, vertically stacked heterojunction of lead iodide (PbI₂)/graphene on a flexible polyethylene terephthalate (PET) film by vapor deposition of PbI₂ on graphene/PET substrate at a temperature lower than 200 °C is demonstrated. This film is subsequently used to fabricate bendable graphene/PbI₂/graphene sandwiched photodetectors, which exhibit high responsivity (45 A W^?1 cm^?2), fast response (35 µs rise, 20 µs decay), and high‐resolution imaging capability (1 µm). This study may pave a facile pathway for scalable production of high‐performance flexible devices.     

Highly Flexible and Transparent Multilayer MoS2 Transistors with Graphene Electrodes

A highly flexible and transparent transistor is developed based on an exfoliated MoS₂ channel and CVD‐grown graphene source/drain electrodes. Introducing the 2D nanomaterials provides a high mechanical flexibility, optical transmittance (～74%), and current on/off ratio (>10⁴) with an average field effect mobility of ～4.7 cm² V^?1 s^?1, all of which cannot be achieved by other transistors consisting of a MoS₂ active channel/metal electrodes or graphene channel/graphene electrodes. In particular, a low Schottky barrier (～22 meV) forms at the MoS₂/graphene interface, which is comparable to the MoS₂/metal interface. The high stability in electronic performance of the devices upon bending up to ±2.2 mm in compressive and tensile modes, and the ability to recover electrical properties after degradation upon annealing, reveal the efficacy of using 2D materials for creating highly flexible and transparent devices.