Synchronous Growth of High‐Quality Bilayer Bernal Graphene: From Hexagonal Single‐Crystal Domains to Wafer‐Scale Homogeneous Films

The precise control of the domain structure, layer thickness, and stacking order of graphene has attracted intense interest because of its great potential for nanoelectronics applications. Much effort has been devoted to synthesize semiconducting Bernal (AB)‐stacked bilayer graphene because of its tunable band structure and electronic properties that are unavailable to single‐layer graphene. However, fast growth of large‐scale bilayer graphene sheets with a high AB‐stacking ratio and high mobility on copper poses a tremendous challenge, which has to overcome the self‐limiting effect. This study reports a low‐cost but facile method to rapidly synthesize bilayer Bernal graphene by atmospheric pressure chemical vapor deposition using polystyrene as the feedstock. The bilayer graphene grains and continuous film obtained are of high quality and exhibit field‐effect hole mobilities as high as 5700 and 2200 cm² V^?1 s^?1 at room temperature, respectively. In addition, a synchronous growth mechanism of bilayer graphene is revealed by monitoring the growth process, resulting in a high surface coverage of nearly 100% for a near‐perfect AB‐stacking order. This new synthesis route is significant for industrial application of bilayer graphene and investigation of the growth mechanism of graphene by the chemical vapor deposition process.     

Triangular Graphene Grain Growth on Cube‐Textured Cu Substrates

The growth of graphene has been carried out on cube‐textured (100) oriented Cu (CTO‐Cu) foils using chemical vapor deposition (CVD). Well‐aligned triangular grains self‐assembled on CTO‐Cu during CVD heating in flowing hydrogen. The nucleation of triangular graphene grains has been confirmed. This demonstrates that the shape and possible alignment of the graphene grains can potentially be tuned by changing the properties of the substrate, which should ultimately lead to improved electrical properties of the graphene. This type of graphene nucleation and alignment is novel and has not been observed in previous studies on other copper foil samples.     

Autonomously Controlled Homogenous Growth of Wafer‐Sized High‐Quality Graphene via a Smart Janus Substrate

The work reports a new method for large‐area growth of graphene films, which have been predicted to have novel and broad applications in the future. While chemical vapor deposition (CVD) is currently the preferred method, it suffers from a rather narrow processing window, and there is also much to be desired in the electrical properties of the CVD films. A new method for large‐area growth of graphene films is reported to overcome the narrow processing window of the CVD method. A composite substrate made of a C‐dissolving top (Ni) layer and a C‐rejecting bottom (Cu) layer is designed, which evolves into a C‐rejecting mixture, to autonomously regulate the C content at an elevated yet stable level at and near the surface over an extended duration. This “smart” substrate promotes graphene formation over a wide temperature‐gas composition window, leading to reliable growth of wafer‐sized graphene films of defined layer‐thickness and superior electrical–optical properties. This “smart”‐substrate strategy can also be implemented on Si and SiO₂ supports, paving the way toward the direct fabrication of large area, graphene‐enabled electronic and photonic devices.     

Layer‐Controlled and Wafer‐Scale Synthesis of Uniform and High‐Quality Graphene Films on a Polycrystalline Nickel Catalyst

Chemical vapor deposition (CVD) provides a synthesis route for large‐area and high‐quality graphene films. However, layer‐controlled synthesis remains a great challenge on polycrystalline metallic films. Here, a facile and viable synthesis of layer‐controlled and high‐quality graphene films on wafer‐scale Ni surface by the sequentially separated steps of gas carburization, hydrogen exposure, and segregation is developed. The layer numbers of graphene films with large domain sizes are controlled precisely at ambient pressure by modulating the simplified CVD process conditions and hydrogen exposure. The hydrogen exposure assisted with a Ni catalyst plays a critical role in promoting the preferential segregation through removing the carbon layers on the Ni surface and reducing carbon content in the Ni. Excellent electrical and transparent conductive performance, with a room‐temperature mobility of ≈3000 cm² V^?1 s^?1 and a sheet resistance as low as ≈100 Ω per square at ≈90% transmittance, of the twisted few‐layer grapheme films grown on the Ni catalyst is demonstrated.     

Metal‐Free Growth of Nanographene on Silicon Oxides for Transparent Conducting Applications

Conventional methods to prepare large‐area graphene for transparent conducting electrodes involve the wet etching of the metal catalyst and the transfer of the graphene film, which can degrade the film through the creation of wrinkles, cracks, or tears. The resulting films may also be obscured by residual metal impurities and polymer contaminants. Here, it is shown that direct growth of large‐area flat nanographene films on silica can be achieved at low temperature (400 °C) by chemical vapor deposition without the use of metal catalysts. Raman spectroscopy and TEM confirm the formation of a hexagonal atomic network of sp²‐bonded carbon with a domain size of about 3–5 nm. Further spectroscopic analysis reveals the formation of SiC between the nanographene and SiO₂, indicating that SiC acts as a catalyst. The optical transmittance of the graphene films is comparable with transferred CVD graphene grown on Cu foils. Despite the fact that the electrical conductivity is an order of magnitude lower than CVD graphene grown on metals, the sheet resistance remains 1–2 orders of magnitude better than well‐reduced graphene oxides.     

Non‐Invasive High‐Throughput Metrology of Functionalized Graphene Sheets

The utilization of fluorescence quenching microscopy (FQM) for quick visualization of chemical functionalization in relatively large regions of graphene, grown via chemical vapor deposition (CVD), is discussed. Through reactive ion plasma etching, patterns of p‐type CVD‐grown graphene functionalized with fluorine are generated. 4‐(dicyanomethylene)‐2‐methyl‐6‐(4‐dimethylaminostyryl)‐4H‐pyran (DCM) is used as the fluorescent agent. The emission of DCM is quenched to a different extent by fluorinated and pristine graphene, which provides the fluorescence‐imaging contrast essential for this metrology. To probe the functionalized surface patterns with DCM, the dye is dispersed in polymethylmethacrylate (PMMA) then the graphene surface is coated, forming a 30‐nm‐thick DCM‐PMMA layer. Fluorescence images of dye‐coated graphene distinctly reveal the difference between the chemically treated and as‐grown regions. The pristine graphene quenches the DCM emission more efficiently than the fluorinated graphene. Therefore, the regions with pristine graphene appear darker on the fluorescence images than the regions with fluorinated graphene, enabling large‐scale mapping of the functionalized regions in CVD grown graphene sheets Due to its simplicity and consistent results, FQM is now poised for widespread adoption by graphene manufacturers as a basis for facile and high throughput metrology of large‐scale graphene sheets.     

Co‐Percolating Graphene‐Wrapped Silver Nanowire Network for High Performance,Highly Stable,Transparent Conducting Electrodes

Transparent conducting electrodes (TCEs) require high transparency and low sheet resistance for applications in photovoltaics, photodetectors, flat panel displays, touch screen devices and imagers. Indium tin oxide (ITO), or other transparent conductive oxides, have typically been used, and provide a baseline sheet resistance (R_S) vs. transparency (T) relationship. However, ITO is relatively expensive (due to limited abundance of Indium), brittle, unstable, and inflexible; moreover, ITO transparency drops rapidly for wavelengths above 1000 nm. Motivated by a need for transparent conductors with comparable (or better) R_S at a given T, as well as flexible structures, several alternative material systems have been investigated. Single‐layer graphene (SLG) or few‐layer graphene provide sufficiently high transparency (≈97% per layer) to be a potential replacement for ITO. However, large‐area synthesis approaches, including chemical vapor deposition (CVD), typically yield films with relatively high sheet resistance due to small grain sizes and high‐resistance grain boundaries (HGBs). In this paper, we report a hybrid structure employing a CVD SLG film and a network of silver nanowires (AgNWs): R_S as low as 22 Ω/□ (stabilized to 13 Ω/□ after 4 months) have been observed at high transparency (88% at λ = 550 nm) in hybrid structures employing relatively low‐cost commercial graphene with a starting R_S of 770 Ω/□. This sheet resistance is superior to typical reported values for ITO, comparable to the best reported TCEs employing graphene and/or random nanowire networks, and the film properties exhibit impressive stability under mechanical pressure, mechanical bending and over time. The design is inspired by the theory of a co‐percolating network where conduction bottlenecks of a 2D film (e.g., SLG, MoS₂) are circumvented by a 1D network (e.g., AgNWs, CNTs) and vice versa. The development of these high‐performance hybrid structures provides a route towards robust, scalable and low‐cost approaches for realizing high‐performance TCE.     

Dirac Cone Spin Polarization of Graphene by Magnetic Insulator Proximity Effect Probed with Outermost Surface Spin Spectroscopy

The effects of the proximity contact with magnetic insulator on the spin‐dependent electronic structure of graphene are explored for the heterostructure of single‐layer graphene (SLG) and yttrium iron garnet Y₃Fe₅O₁₂ (YIG) by means of outermost surface spin spectroscopy using a spin‐polarized metastable He atom beam. In the SLG/YIG heterostructure, the Dirac cone electrons of graphene are found to be negatively spin polarized in parallel to the minority spins of YIG with a large polarization degree, without giving rise to significant changes in the π band structure. Theoretical calculations reveal the electrostatic interfacial interactions providing a strong physical adhesion and the indirect exchange interaction causing the spin polarization of SLG at the interface with YIG. The Hall device of the SLG/YIG heterostructure exhibits a nonlinear Hall resistance attributable to the anomalous Hall effect, implying the extrinsic spin–orbit interactions as another manifestation of the proximity effect.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

Synergistic Roll‐to‐Roll Transfer and Doping of CVD‐Graphene Using Parylene for Ambient‐Stable and Ultra‐Lightweight Photovoltaics

A roll‐to‐roll (R2R) transfer technique is employed to improve the electrical properties of transferred graphene on flexible substrates using parylene as an interfacial layer. A layer of parylene is deposited on graphene/copper (Cu) foils grown by chemical vapor deposition and are laminated onto ethylene vinyl acetate (EVA)/poly(ethylene terephthalate). Then, the samples are delaminated from the Cu using an electrochemical transfer process, resulting in flexible and conductive substrates with sheet resistances of below 300 Ω sq^?1, which is significantly better (fourfold) than the sample transferred by R2R without parylene (1200 Ω sq^?1). The characterization results indicate that parylene C and D dope graphene due to the presence of chlorine atoms in their structure, resulting in higher carrier density and thus lower sheet resistance. Density functional theory calculations reveal that the binding energy between parylene and graphene is stronger than that of EVA and graphene, which may lead to less tear in graphene during the R2R transfer. Finally, organic solar cells are fabricated on the ultrathin and flexible parylene/graphene substrates and an ultra‐lightweight device is achieved with a power conversion efficiency of 5.86%. Additionally, the device shows a high power per weight of 6.46 W g^?1 with superior air stability.     

Multifunctional Three‐Dimensional T‐Junction Graphene Micro‐Wells: Energy‐Efficient,Plasma‐Enabled Growth and Instant Water‐Based Transfer for Flexible Device Applications

The “third‐generation” 3D graphene structures, T‐junction graphene micro‐wells (T‐GMWs) are produced on cheap polycrystalline Cu foils in a single‐step, low‐temperature (270 °C), energy‐efficient, and environment‐friendly dry plasma‐enabled process. T‐GMWs comprise vertical graphene (VG) petal‐like sheets that seemlessly integrate with each other and the underlying horizontal graphene sheets by forming T‐junctions. The microwells have the pico‐to‐femto‐liter storage capacity and precipitate compartmentalized PBS crystals. The T‐GMW films are transferred from the Cu substrates, without damage to the both, in de‐ionized or tap water, at room temperature, and without commonly used sacrificial materials or hazardous chemicals. The Cu substrates are then re‐used to produce similar‐quality T‐GMWs after a simple plasma conditioning. The isolated T‐GMW films are transferred to diverse substrates and devices and show remarkable recovery of their electrical, optical, and hazardous NO₂ gas sensing properties upon repeated bending (down to 1 mm radius) and release of flexible trasparent display plastic substrates. The plasma‐enabled mechanism of T‐GMW isolation in water is proposed and supported by the Cu plasma surface modification analysis. Our GMWs are suitable for various optoelectronic, sesning, energy, and biomedical applications while the growth approach is potentially scalable for future pilot‐scale industrial production.     

Homogeneous Optical and Electronic Properties of Graphene Due to the Suppression of Multilayer Patches During CVD on Copper Foils

A synthesis method of strictly monolayer and fully homogeneous graphene across tens of centimeter squares, by chemical vapour deposition onto standard copper foils, is presented. The growth technique involves cyclic injection of a carbon precursor separated by idle times with constant hydrogen exposure. The formation of spurious multilayer patches, which accompanies the standard growth techniques based on continuous exposure to methane, is inhibited here, in a broad range of pressure and gas composition, including in two pressure regimes which are known to yield distinctive grain morphologies (dendritic versus hexagonal). Raman spectra confirm the absence of defects within the graphene films. A mechanism for growth/suppression of the multilayer patches based on the carbon storage at defective regions is proposed. The importance of multilayer suppression is highlighted in a comparative study showing the detrimental effect of patches on the performances of graphene transistors and on the optical transparency of stacked layers. The full‐layer graphene sheets are superiorly homogeneous in terms of their optical and electronic properties, and are thus suited for applications for high‐density integration as well as transparent electrodes with spatially continuous optical absorbance. Graphene transistors fabricated by the pulsed CVD method exhibit room‐temperature mobilities with a mean value of 5000 cm² V^?1 s^?1.     

Large Scale Graphene/Hexagonal Boron Nitride Heterostructure for Tunable Plasmonics

Vertical integration of hexagonal boron nitride (h‐BN) and graphene for the fabrication of vertical field‐effect transistors or tunneling diodes has stimulated intense interest recently due to the enhanced performance offered by combining an ultrathin dielectric with a semi‐metallic system. Wafer scale fabrication and processing of these heterostructures is needed to make large scale integrated circuitry. In this work, by using remote discharged, radio‐frequency plasma chemical vapor deposition, wafer scale, high quality few layer h‐BN films are successfully grown. By using few layer h‐BN films as top gate dielectric material, the plasmon energy of graphene can be tuned by electrostatic doping. An array of graphene/h‐BN vertically stacked micrometer‐sized disks is fabricated by lithography and transfer techniques, and infrared spectroscopy is used to observe the modes of tunable graphene plasmonic absorption as a function of the repeating (G/h‐BN)_n units in the vertical stack. Interestingly, the plasmonic resonances can be tuned to higher frequencies with increasing layer thickness of the disks, showing that such vertical stacking provides a viable strategy to provide wide window tuning of the plasmons beyond the limitation of the monolayer.     

X‐Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects

Chemical doping of graphene represents a powerful means of tailoring its electronic properties. Synchrotron‐based X‐ray spectroscopy offers an effective route to investigate the surface electronic and chemical states of functionalizing dopants. In this work, a suite of X‐ray techniques is used, including near edge X‐ray absorption fine structure spectroscopy, X‐ray photoemission spectroscopy, and photoemission threshold measurements, to systematically study plasma‐based chlorinated graphene on different substrates, with special focus on its dopant concentration, surface binding energy, bonding configuration, and work function shift. Detailed spectroscopic evidence of C–Cl bond formation at the surface of single layer graphene and correlation of the magnitude of p‐type doping with the surface coverage of adsorbed chlorine is demonstrated for the first time. It is shown that the chlorination process is a highly nonintrusive doping technology, which can effectively produce strongly p‐doped graphene with the 2D nature and long‐range periodicity of the electronic structure of graphene intact. The measurements also reveal that the interaction between graphene and chlorine atoms shows strong substrate effects in terms of both surface coverage and work function shift.     

Wide‐Area Strain Sensors based upon Graphene‐Polymer Composite Coatings Probed by Raman Spectroscopy

Functional graphene optical sensors are now viable due to the recent developments in hand‐held Raman spectroscopy and the chemical vapor deposition (CVD) of graphene films. Herein, the strain in graphene/poly (methyl methacrylate) sensor coatings is followed using Raman band shifts. The performance of an “ideal” mechanically‐exfoliated single crystal graphene flake is compared to a scalable CVD graphene film. The dry‐transferred mechanically exfoliated sample has no residual stresses, whereas the CVD sample is in compression following the solvent evaporation during its transfer. The behavior of the sensors under cyclic deformation shows an initial breakdown of the graphene‐polymer interface with the interface then stabilizing after several cycles. The Raman 2D band shift rates per unit strain of the exfoliated graphene are ≈35% higher than CVD graphene making the former more strain sensitive. However, for practical wide‐area applications, CVD graphene coatings are still viable candidates as a Raman system can be used to read the strain in any 5 μm diameter spot in the coating to an absolute accuracy of ≈0.01% strain and resolution of ≈27 microstrains (μs), which compares favorably to commercial photoelastic systems.     

Homogeneous CoO on Graphene for Binder‐Free and Ultralong‐Life Lithium Ion Batteries

Ultralong cycle life, high energy, and power density rechargeable lithium‐ion batteries are crucial to the ever‐increasing large‐scale electric energy storage for renewable energy and sustainable road transport. However, the commercial graphite anode cannot perform this challenging task due to its low theoretical capacity and poor rate‐capability performance. Metal oxides hold much higher capacity but still are plagued by low rate capability and serious capacity degradation. Here, a novel strategy is developed to prepare binder‐free and mechanically robust CoO/graphene electrodes, wherein homogenous and full coating of β‐Co(OH)₂ nanosheets on graphene, through a novel electrostatic induced spread growth method, plays a key role. The combined advantages of large 2D surface and moderate inflexibility of the as‐obtained β‐Co(OH)₂/graphene hybrid enables its easy coating on Cu foil by a simple layer‐by‐layer stacking process. Devices made with these electrodes exhibit high rate capability over a temperature range from 0 to 55 °C and, most importantly, maintain excellent cycle stability up to 5000 cycles even at a high current density.     

Schottky‐Barrier‐Controllable Graphene Electrode to Boost Rectification in Organic Vertical P–N Junction Photodiodes

Monolayer graphene is used as an electrode to develop novel electronic device architectures that exploit the unique, atomically thin structure of the material with a low density of states at its charge neutrality point. For example, a single semiconductor layer stacked onto graphene can provide a semiconductor–electrode junction with a tunable injection barrier, which is the basis for a primitive transistor architecture known as the Schottky barrier field‐effect transistor. This work demonstrates the next level of complexity in a vertical graphene–semiconductor architecture. Specifically, an organic vertical p‐n junction (p‐type pentacene/n‐type N,N′‐dioctyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C₈)) on top of a graphene electrode constituting a novel gate‐tunable photodiode device structure is fabricated. The model device confirms that controlling the Schottky barrier height at the pentacene–graphene junction can (i) suppress the dark current density and (ii) enhance the photocurrent of the device, both of which are critical to improve the performance of a photodiode.     

Growth and Isolation of Large Area Boron‐Doped Nanocrystalline Diamond Sheets: A Route toward Diamond‐on‐Graphene Heterojunction

Many material device applications would benefit from thin diamond coatings, but current growth techniques, such as chemical vapor deposition (CVD) or atomic layer deposition require high substrate and gas‐phase temperatures that would destroy the device being coated. The development of freestanding, thin boron‐doped diamond nanosheets grown on tantalum foil substrates via microwave plasma‐assisted CVD is reported. These diamond sheets (measuring up to 4 × 5 mm in planar area, and 300–600 nm in thickness) are removed from the substrate using mechanical exfoliation and then transferred to other substrates, including Si/SiO₂ and graphene. The electronic properties of the resulting diamond nanosheets and their dependence on the free‐standing growth, the mechanical exfoliation and transfer processes, and ultimately on their composition are characterized. To validate this, a prototypical diamond nanosheet–graphene field effect transistor‐like (DNGfet) device is developed and its electronic transport properties are studied as a function of temperature. The resulting DNGfet device exhibits thermally activated transport (thermionic conductance) above 50 K. Below 50 K a transition to variable range hopping is observed. These findings demonstrate the first step towards a low‐temperature diamond‐based transistor.     

Direct Growth of Edge‐Rich Graphene with Tunable Dielectric Properties in Porous Si3N4 Ceramic for Broadband High‐Performance Microwave Absorption

High‐performance graphene microwave absorption materials are highly desirable in daily life and some extreme situations. A simple technique for the direct growth of graphene as absorption fillers in wave‐transmitting matrices is of paramount importance to bring it to real‐world application. Herein, a simple chemical vapor deposition (CVD) route for the direct growth of edge‐rich graphene (ERG) with tailored structures and tunable dielectric properties in porous Si₃N₄ ceramics using only methyl alcohol (CH₃OH) as precursor is reported. The large O/C atomic ratio of CH₃OH helps to build a mild oxidizing atmosphere and leads to a unique structure featuring open graphite nanosteps and freestanding nanoplanes, endowing the ERG/Si₃N₄ hybrid with an appropriate balance between good impedance matching and strong loss capacity. Accordingly, the prepared materials exhibit superior electromagnetic wave absorption, far surpassing that of traditional CVD graphene and reduced graphene oxide‐based materials, achieving an effective absorption bandwidth of 4.2 GHz covering the entire X band, with a thickness of 3.75 mm and a negligibly low loading content of absorbents. The results provide new insights for developing novel microwave absorption materials with strong reflection loss and wide absorption frequency range.     

A Generic Synthetic Approach to Large‐Scale Pristine‐Graphene/Metal‐Nanoparticles Hybrids

The homogeneous attachment of metal‐nanoparticles (metal‐NPs) on pristine‐graphene surface to construct pristine‐graphene/metal‐NPs hybrids is highly expected for application in many fields such as transparent electrodes and conductive composites. However, it remains a great challenge since the pristine‐graphene is highly hydrophobic. Here, an environmentally friendly generic synthetic approach to large‐scale pristine‐graphene/metal‐NPs hybrids is presented, by a combinatorial process of exfoliating expanded graphite in N‐methyl pyrrolidone via sonication and centrifugation to achieve the pristine‐graphene, and attaching pre‐synthesized metal‐NPs on the pristine‐graphene in ethanol via van der Waals interactions between the metal‐NPs and the pristine‐graphene. Nanoparticles of different metals (such as Ag, Au, and Pd) with various morphologies (such as sphere, cube, plate, multi‐angle, and spherical‐particle assembling) can be homogeneously attached on the defect‐free pristine‐graphene with controlled packing densities. Both the pristine‐graphene and the metal‐NPs preserve their original intrinsic structures. The as‐synthesized pristine‐graphene/Ag‐NPs hybrids show very high surface‐enhanced Raman scattering activity due to the combined effects of large surface area of the pristine‐graphene to adsorb more target molecules and the electromagnetic enhancement of the Ag‐NPs. This large‐scale synthesis of the pristine‐graphene/metal‐NPs hybrids with tunable shape and packing density of metal‐NPs opens up opportunities for fundamental research and potential applications ranging from devices to transparent electrodes and conductive composites.