Graphene Glass from Direct CVD Routes: Production and Applications

Recently, direct chemical vapor deposition (CVD) growth of graphene on various types of glasses has emerged as a promising route to produce graphene glass, with advantages such as tunable quality, excellent film uniformity and potential scalability. Crucial to the performance of this graphene‐coated glass is that the outstanding properties of graphene are fully retained for endowing glass with new surface characteristics, making direct‐CVD‐derived graphene glass versatile enough for developing various applications for daily life. Herein, recent advances in the synthesis of graphene glass, particularly via direct CVD approaches, are presented. Key applications of such graphene materials in transparent conductors, smart windows, simple heating devices, solar‐cell electrodes, cell culture medium, and water harvesters are also highlighted.     

Direct CVD Graphene Growth on Semiconductors and Dielectrics for Transfer‐Free Device Fabrication

Graphene is the most broadly discussed and studied two‐dimensional material because of its preeminent physical, mechanical, optical, and thermal properties. Until now, metal‐catalyzed chemical vapor deposition (CVD) has been widely employed for the scalable production of high‐quality graphene. However, in order to incorporate the graphene into electronic devices, a transfer process from metal substrates to targeted substrates is inevitable. This process usually results in contamination, wrinkling, and breakage of graphene samples ‐ undesirable in graphene‐based technology and not compatible with industrial production. Therefore, direct graphene growth on desired semiconductor and dielectric substrates is considered as an effective alternative. Over the past years, there have been intensive investigations to realize direct graphene growth using CVD methods without the catalytic role of metals. Owing to the low catalytic activity of non‐metal substrates for carbon precursor decomposition and graphene growth, several strategies have been designed to facilitate and engineer graphene fabrication on semiconductors and insulators. Here, those developed strategies for direct CVD graphene growth on semiconductors and dielectrics for transfer‐free fabrication of electronic devices are reviewed. By employing these methods, various graphene‐related structures can be directly prepared on desired substrates and exhibit excellent performance, providing versatile routes for varied graphene‐based materials fabrication.     

Controllable Growth of Graphene on Liquid Surfaces

Controllable fabrication of graphene is necessary for its practical application. Chemical vapor deposition (CVD) approaches based on solid metal substrates with morphology‐rich surfaces, such as copper (Cu) and nickel (Ni), suffer from the drawbacks of inhomogeneous nucleation and uncontrollable carbon precipitation. Liquid substrates offer a quasiatomically smooth surface, which enables the growth of uniform graphene layers. The fast surface diffusion rates also lead to unique growth and etching kinetics for achieving graphene grains with novel morphologies. The rheological surface endows the graphene grains with self‐adjusted rotation, alignment, and movement that are driven by specific interactions. The intermediary‐free transfer or the direct growth of graphene on insulated substrates is demonstrated using liquid metals. Here, the controllable growth process of graphene on a liquid surface to promote the development of attractive liquid CVD strategies is in focus. The exciting progress in controlled growth, etching, self‐assembly, and delivery of graphene on a liquid surface is presented and discussed in depth. In addition, prospects and further developments in these exciting fields of graphene growth on a liquid surface are discussed.     

Germanium‐Assisted Direct Growth of Graphene on Arbitrary Dielectric Substrates for Heating Devices

Direct growth of graphene on dielectric substrates is a prerequisite to the development of graphene‐based electronic and optoelectronic devices. However, the current graphene synthesis methods on dielectric substrates always involve a metal contamination problem, and the direct production of graphene patterns still remains unattainable and challenging. Herein, a semiconducting, germanium (Ge)‐assisted, chemical vapor deposition approach is proposed to produce monolayer graphene directly on arbitrary dielectric substrates. By the prepatterning of a catalytic Ge layer, the graphene with desired pattern can be achieved conveniently and readily. Due to the catalysis of Ge, monolayer graphene is able to form on Ge‐covered dielectric substrates including SiO₂/Si, quartz glass, and sapphire substrates. Optimization of the process parameters leads to complete sublimation of the catalytic Ge layer during or immediately after formation of the monolayer graphene, enabling direct deposition of large‐area and continuous graphene on dielectric substrates. The large‐area, highly conductive graphene synthesized on a transparent dielectric substrate using the proposed approach has exhibited a wide range of applications, including in both defogger and thermochromic displays, as already successfully demonstrated here.     

H2O‐Etchant‐Promoted Synthesis of High‐Quality Graphene on Glass and Its Application in See‐Through Thermochromic Displays

Direct growth of graphene on glass can bring an innovative revolution by coupling the complementary properties of traditional glass and modern graphene (such as transparency and conductivity), offering brand new daily‐life related applications. However, preparation of high‐quality graphene on nonmetallic glass is still challenging. Herein, the direct route of low sheet resistance graphene on glass is reported by using in situ‐introduced water as a mild etchant and methane as a carbon precursor via chemical vapor deposition. The derived graphene features with large domain sizes and few amorphous carbon impurities. Intriguingly, the sheet resistance of graphene on glass is dramatically lowered down to ≈1170 Ω sq^?1 at the optical transmittance ≈93%, ≈20% of that derived without the water etchant. Based on the highly conductive and optical transparent graphene on glass, a see‐through thermochromic display is thus fabricated with transparent graphene glass as a heater. This work can motivate further investigations of the direct synthesis of high‐quality graphene on functional glass and its versatile applications in transparent electronic devices or displays.     

Graphene Single Crystals: Size and Morphology Engineering

Recently developed chemical vapor deposition (CVD) is considered as an effective way to large‐area and high‐quality graphene preparation due to its ultra‐low cost, high controllability, and high scalability. However, CVD‐grown graphene film is polycrystalline, and composed of numerous grains separated by grain boundaries, which are detrimental to graphene‐based electronics. Intensive investigations have been inspired on the controlled growth of graphene single crystals with the absence of intrinsic defects. As the two most concerned parameters, the size and morphology serve critical roles in affecting properties and understanding the growth mechanism of graphene crystals. Therefore, a precise tuning of the size and morphology will be of great significance in scale‐up graphene production and wide applications. Here, recent advances in the synthesis of graphene single crystals on both metals and dielectric substrates by the CVD method are discussed. The review mainly covers the size and morphology engineering of graphene single crystals. Furthermore, recent progress in the growth mechanism and device applications of graphene single crystals are presented. Finally, the opportunities and challenges are discussed.     

Graphene on Group‐IV Elementary Semiconductors: The Direct Growth Approach and Its Applications

Since the first development of large‐area graphene synthesis by the chemical vapor deposition (CVD) method in 2009, CVD‐graphene has been considered to be a key material in the future electronics, energy, and display industries, which require transparent, flexible, and stretchable characteristics. Although many graphene‐based prototype applications have been demonstrated, several important issues must be addressed in order for them to be compatible with current complementary metal‐oxide‐semiconductor (CMOS)‐based manufacturing processes. In particular, metal contamination and mechanical damage, caused by the metal catalyst for graphene growth, are known to cause severe and irreversible deterioration in the performance of devices. The most effective way to solve the problems is to grow the graphene directly on the semiconductor substrate. Herein, recent advances in the direct growth of graphene on group‐IV semiconductors are reviewed, focusing mainly on the growth mechanism and initial growth behavior when graphene is synthesized on Si and Ge. Furthermore, recent progress in the device applications of graphene with Si and Ge are presented. Finally, perspectives for future research in graphene with a semiconductor are discussed.     

Electron Transfer Directed Antibacterial Properties of Graphene Oxide on Metals

Nanomaterials such as silver nanoparticles and graphene‐based composites are known to exhibit biocidal activities. However, interactions with surrounding medium or supporting substrates can significantly influence this activity. Here, it is shown that superior antimicrobial properties of natural shellac‐derived graphene oxide (GO) coatings is obtained on metallic films, such as Zn, Ni, Sn, and steel. It is also found that such activities are directly correlated to the electrical conductivity of the GO‐metal systems; the higher the conductivity the better is the antibacterial activity. GO‐metal substrate interactions serve as an efficient electron sink for the bacterial respiratory pathway, where electrons modify oxygen containing functional groups on GO surfaces to generate reactive oxygen species (ROS). A concerted effect of nonoxidative electron transfer mechanism and consequent ROS mediated oxidative stress to the bacteria result in an enhanced antimicrobial action of naturally derived GO‐metal films. The lack of germicidal effect in exposed cells for GO supported on electrically nonconductive substrates such as glass corroborates the above hypothesis. The results can lead to new GO coated antibacterial metal surfaces important for environmental and biomedical applications.     

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.     

Direct Growth of Highly Stable Patterned Graphene on Dielectric Insulators using a Surface‐Adhered Solid Carbon Source

A novel method is described for the direct growth of patterned graphene on dielectric substrates by chemical vapor deposition (CVD) in the presence of Cu vapor and using a solid aromatic carbon source, 1,2,3,4‐tetraphenylnapthalene (TPN), as the precursor. The UV/O₃ treatment of the TPN film both crosslinks TPN and results in a strong interaction between the substrate and the TPN that prevents complete sublimation of the carbon source from the substrate during CVD. Substrate‐adhered crosslinked TPN is successfully converted to graphene on the substrate without any organic contamination. The graphene synthesized by this method shows excellent mechanical and chemical stability. This process also enables the simultaneous patterning of graphene materials, which can thus be used as transparent electrodes for electronic devices. The proposed method for the synthesis directly on substrates of patterned graphene is expected to have wide applications in organic and soft hybrid electronics.     

Fast and uniform growth of graphene glass using confined-flow chemical vapor deposition and its unique applications

Fast and uniform growth of high-quality graphene on conventional glass is of great importance for practical applications of graphene glass. We report herein a confined-flow chemical vapor deposition (CVD) approach for the high-efficiency fabrication of graphene glass. The key feature of our approach is the fabrication of a 2–4 μm wide gap above the glass substrate, with plenty of stumbling blocks; this gap was found to significantly increase the collision probability of the carbon precursors and reactive fragments between one another and with the glass surface. As a result, the growth rate of graphene glass increased remarkably, together with an improvement in the growth quality and uniformity as compared to those in the conventional gas flow CVD technique. These high-quality graphene glasses exhibited an excellent defogging performance with much higher defogging speed and higher stability compared to those previously reported. The graphene sapphire glass was found to be an ideal substrate for growing uniform and ultra-smooth aluminum nitride thin films without the tedious pre-deposition of a buffer layer. The presented confined-flow CVD approach offers a simple and low-cost route for the mass production of graphene glass, which is believed to promote the practical applications of various graphene glasses.

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Fast Batch Production of High‐Quality Graphene Films in a Sealed Thermal Molecular Movement System

Chemical vapor deposition (CVD) growth of high‐quality graphene has emerged as the most promising technique in terms of its integrated manufacturing. However, there lacks a controllable growth method for producing high‐quality and a large‐quantity graphene films, simultaneously, at a fast growth rate, regardless of roll‐to‐roll (R2R) or batch‐to‐batch (B2B) methods. Here, a stationary‐atmospheric‐pressure CVD (SAPCVD) system based on thermal molecular movement, which enables fast B2B growth of continuous and uniform graphene films on tens of stacked Cu(111) foils, with a growth rate of 1.5 µ m s^?1, is demonstrated. The monolayer graphene of batch production is found to nucleate from arrays of well‐aligned domains, and the films possess few defects and exhibit high carrier mobility up to 6944 cm² V^?1 s^?1 at room temperature. The results indicate that the SAPCVD system combined with single‐domain Cu(111) substrates makes it possible to realize fast batch‐growth of high‐quality graphene films, which opens up enormous opportunities to use this unique 2D material for industrial device applications.     

One Second Formation of Large Area Graphene on a Conical Tip Surface via Direct Transformation of Surface Carbide

Graphene functionalized nanotips are expected to possess promising potential for various applications based on the outstanding electrical and mechanical properties of graphene. However, current methods, usually requiring a high growth temperature and identical crystal surface to match graphene lattice, are suitable for graphene formation on a flat surface. It remains a big challenge to grow graphene on a nanosized convex surface and fabricate functionalized nanotips with high quality graphene at the apex. In this work, a novel ultrafast annealing method is developed for growing large area graphene on Ni nanotips within 1–2 s. Few layered or multiple layered graphene is presented on the apex or sidewall of the conical tip surface. Direct experimental evidences support that thus‐produced graphene is formed via the direct conversion of nickel carbide at the outer surface under the instantaneous high temperature, which is different from the conventional segregation mechanism. This newly developed ultrafast method provides a new route to produce graphene efficiently and economically, promising for both convex surfaces and flat substrates. Moreover, the graphene functionalized nanotips exhibit a great potential for nanoelectrical measurements and conductive scanning probe microscopy (SPM) applications.     

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.     

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.     

“Snowing” Graphene using Microwave Ovens

Developing a simple and industrially scalable method to produce graphene with high quality and low cost will determine graphene's future. The two conventional approaches, chemical vapor deposition and liquid‐phase exfoliation, require either costly substrates with limited production rate or complicated post treatment with limited quality, astricting their development. Herein, an extremely simple process is presented for synthesizing high quality graphene at low‐cost in the gas phase, similar to “snowing,” which is catalyst‐free, substrate‐free, and scalable. This is achieved by utilizing corona discharge of SiO₂/Si in an ordinary household microwave oven at ambient pressure. High quality graphene flakes can “snow” on any substrate, with thin‐flakes even down to the monolayer. In particular, a high yield of ≈6.28% or a rate of up to ≈0.11 g h^?1 can be achieved in a conventional microwave oven. It is demonstrated that the snowing process produces foam‐like, fluffy, 3D macroscopic architectures, which are further used in strain sensors for achieving high sensitivity (average gauge factor ≈ 171.06) and large workable strain range (0%–110%) simultaneously. It is foreseen that this facile and scalable strategy can be extended for “snowing” other functional 2D materials, benefiting their low‐cost production and wide applications.     

Remote catalyzation for direct formation of graphene layers on oxides

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth.     

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.     

Direct Synthesis of Large‐Area 2D Mo2C on In Situ Grown Graphene

As a new member of the MXene group, 2D Mo₂C has attracted considerable interest due to its potential application as electrodes for energy storage and catalysis. The large‐area synthesis of Mo₂C film is needed for such applications. Here, the one‐step direct synthesis of 2D Mo₂C‐on‐graphene film by molten copper‐catalyzed chemical vapor deposition (CVD) is reported. High‐quality and uniform Mo₂C film in the centimeter range can be grown on graphene using a Mo–Cu alloy catalyst. Within the vertical heterostructure, graphene acts as a diffusion barrier to the phase‐segregated Mo and allows nanometer‐thin Mo₂C to be grown. Graphene‐templated growth of Mo₂C produces well‐faceted, large‐sized single crystals with low defect density, as confirmed by scanning transmission electron microscopy (STEM) measurements. Due to its more efficient graphene‐mediated charge‐transfer kinetics, the as‐grown Mo₂C‐on‐graphene heterostructure shows a much lower onset voltage for hydrogen evolution reactions as compared to Mo₂C‐only electrodes.     

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.