One‐Step Formation of a Single Atomic‐Layer Transistor by the Selective Fluorination of a Graphene Film

In this study, the scalable and one‐step fabrication of single atomic‐layer transistors is demonstrated by the selective fluorination of graphene using a low‐damage CF₄ plasma treatment, where the generated F‐radicals preferentially fluorinated the graphene at low temperature (<200 °C) while defect formation was suppressed by screening out the effect of ion damage. The chemical structure of the C–F bonds is well correlated with their optical and electrical properties in fluorinated graphene, as determined by X‐ray photoelectron spectroscopy, Raman spectroscopy, and optical and electrical characterizations. The electrical conductivity of the resultant fluorinated graphene (F‐graphene) was demonstrated to be in the range between 1.6 kΩ/sq and 1 MΩ/sq by adjusting the stoichiometric ratio of C/F in the range between 27.4 and 5.6, respectively. Moreover, a unique heterojunction structure of semi‐metal/semiconductor/insulator can be directly formed in a single layer of graphene using a one‐step fluorination process by introducing a Au thin‐film as a buffer layer. With this heterojunction structure, it would be possible to fabricate transistors in a single graphene film via a one‐step fluorination process, in which pristine graphene, partial F‐graphene, and highly F‐graphene serve as the source/drain contacts, the channel, and the channel isolation in a transistor, respectively. The demonstrated graphene transistor exhibits an on‐off ratio above 10, which is 3‐fold higher than that of devices made from pristine graphene. This efficient transistor fabrication method produces electrical heterojunctions of graphene over a large area and with selective patterning, providing the potential for the integration of electronics down to the single atomic‐layer scale.     

Scaly Graphene Oxide/Graphite Fiber Hybrid Electrodes for DNA Biosensors

The demand for a highly sensitive and stable DNA biosensor that can be used for implantable or on‐time monitoring is constantly increasing. In this work, for the first time graphene oxide (GO) sheets are synthesized in situ at the surface of graphite fibers to yield scaly GO/graphite fiber hybrid electrodes. The partially peeled GO sheets, directly connected with the graphite fibers, not only provide a large number of binding sites for single‐stranded DNA, but also favor high electron transfer rates from GO to the graphite fibers. Cyclic voltammetry (CV) confirms that the scaly GO/graphite fiber hybrid electrode has excellent electrochemical activity. As a working electrode in an electrochemical impedance DNA biosensor, the fiber hybrid electrode exhibits high selectivity, sensitivity, and stability. Due to its simplicity, low cost, high stability, small size, and unique microfiber morphology, the scaly GO/graphite fiber hybrid electrode is an excellent candidate for an implantable biosensor. The method developed here could have a profound impact on the design of GO‐based biosensors for DNA detection.     

Graphene‐Based Fibers: A Review

Motivated by their unique structure and excellent properties, significant progress has been made in recent years in the development of graphene‐based fibers (GBFs). Potential applications of GBFs can be found, for instance, in conducting wires, energy storage and conversion devices, actuators, field emitters, solid‐phase microextraction, springs, and catalysis. In contrast to graphene‐based aerogels (GBAs) and membranes (GBMs), GBFs demonstrate remarkable mechanical and electrical properties and can be bent, knotted, or woven into flexible electronic textiles. In this review, the state‐of‐the‐art of GBFs is summarized, focusing on their synthesis, performance, and applications. Future directions of GBF research are also proposed.     

The effect of exfoliation and plasma application on the properties of continuous graphene oxide fiber

This study has been performed on continuous graphene oxide fiber produced by different production parameters which has very large potential application areas such as electronic/smart textiles, sensors, energy. In this study, three different graphene oxide dispersion preparation methods; namely, Modified Hummers, Modified Hummers on exfoliated graphite and Modified Hummers with plasma application; have been used to prepare coagulated continuous graphene oxide fibers. The effect of production parameters on properties of continuous graphene oxide fibers have been measured by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-Ray Photoelectron Microscopy (XPS), tensile tester, electrical conductivity device. It was observed that exfoliation process results with decrease of fiber Tex count, fiber surface roughness, oxygen functional groups and an increase of breaking strength and electrical conductivity, while plasma application results to an increase of surface roughness of fiber, oxygen functional groups and decrease of breaking strength of fiber.     

Breaking the Current‐Retention Dilemma in Cation‐Based Resistive Switching Devices Utilizing Graphene with Controlled Defects

Cation‐based resistive switching (RS) devices, dominated by conductive filaments (CF) formation/dissolution, are widely considered for the ultrahigh density nonvolatile memory application. However, the current‐retention dilemma that the CF stability deteriorates greatly with decreasing compliance current makes it hard to decrease operating current for memory application and increase driving current for selector application. By centralizing/decentralizing the CF distribution, this current‐retention dilemma of cation‐based RS devices is broken for the first time. Utilizing the graphene impermeability, the cation injecting path to the RS layer can be well modulated by structure‐defective graphene, leading to control of the CF quantity and size. By graphene defect engineering, a low operating current (≈1 µA) memory and a high driving current (≈1 mA) selector are successfully realized in the same material system. Based on systematically materials analysis, the diameter of CF, modulated by graphene defect size, is the major factor for CF stability. Breakthrough in addressing the current‐retention dilemma will instruct the future implementation of high‐density 3D integration of RS memory immune to crosstalk issues.     

Vertically Oriented Graphene Nanoribbon Fibers for High‐Volumetric Energy Density All‐Solid‐State Asymmetric Supercapacitors

Graphene fiber based micro‐supercapacitors (GF micro‐SCs) have attracted great attention for their potential applications in portable and wearable electronics. However, due to strong π–π stacking of nanosheets for graphene fibers, the limited ion accessible surface area and slow ion diffusion rate leads to low specific capacitance and poor rate performance. Here, the authors report a strategy for the synthesis of a vertically oriented graphene nanoribbon fiber with highly exposed surface area through confined‐hydrothermal treatment of interconnected graphene oxide nanoribbons and consequent laser irradiation process. As a result, the as‐obtained fiber shows high length specific capacitance of 3.2 mF cm^?1 and volumetric capacitance of 234.8 F cm^?3 at 2 mV s^?1, as well as excellent rate capability and outstanding cycling performance (96% capacitance retention after 10 000 cycles). Moreover, an all‐solid‐state asymmetric supercapacitor based on graphene nanoribbon fiber as negative electrode and MnO₂ coated graphene ribbon fiber as positive electrode, shows high volumetric capacitance and energy density of 12.8 F cm^?3 and 5.7 mWh cm^?3 (normalized to the device volume), respectively, much higher than those of previously reported GF micro‐SCs, as well as a long cycle life with 88% of capacitance retention after 10 000 cycles.     

Controlled,Low‐Temperature Nanogap Propagation in Graphene Using Femtosecond Laser Patterning

Graphene nanogap systems are promising research tools for molecular electronics, memories, and nanodevices. Here, a way to control the propagation of nanogaps in monolayer graphene during electroburning is demonstrated. A tightly focused femtosecond laser beam is used to induce defects in graphene according to selected patterns. It is shown that, contrary to the pristine graphene devices where nanogap position and shape are uncontrolled, the nanogaps in prepatterned devices propagate along the defect line created by the femtosecond laser. Using passive voltage contrast combined with atomic force microscopy, the reproducibility of the process with a 92% success rate over 26 devices is confirmed. Coupling in situ infrared thermography and finite element analysis yields a real‐time estimation of the device temperature during electrical loading. The controlled nanogap formation occurs well below 50 °C when the defect density is high enough. In the perspective of graphene‐based circuit fabrication, the availability of a cold electroburning process is critical to preserve the full circuit from thermal damage.     

Laser‐Assisted Lattice Recovery of Graphene by Carbon Nanodot Incorporation

Producing highly oriented graphene is a major challenge that constrains graphene from fulfilling its full potential in technological applications. The exciting properties of graphene are impeded in practical bulk materials due to lattice imperfections that hinder charge mobility. A simple method to improve the structural integrity of graphene by utilizing laser irradiation on a composite of carbon nanodots (CNDs) and 3D graphene is presented. The CNDs attach themselves to defect sites in the graphene sheets and, upon laser‐assisted reduction, patch defects in the carbon lattice. Spectroscopic experiments reveal graphitic structural recovery of up to 43% and electrical conductivity four times larger than the original graphene. The composites are tested as electrodes in electrochemical capacitors and demonstrate extremely fast RC time constant as low as 0.57 ms. Due to their low defect concentrations, the reduced graphene oxide‐carbon nanodot (rGO‐CND) composites frequency response is sufficiently fast to operate as AC line filters, potentially replacing today's electrolytic capacitors. Using this methodology, demonstrated is a novel line filter with one of the fastest capacitive responses ever reported, and an aerial capacitance of 68.8 mF cm^?2. This result emphasizes the decisive role of structural integrity for optimizing graphene in electronic applications.     

Wetting‐Induced Climbing for Transferring Interfacially Assembled Large‐Area Ultrathin Pristine Graphene Film

Owing to inherent 2D structure, marvelous mechanical, electrical, and thermal properties, graphene has great potential as a macroscopic thin film for surface coating, composite, flexible electrode, and sensor. Nevertheless, the production of large‐area graphene‐based thin film from pristine graphene dispersion is severely impeded by its poor solution processability. In this study, a robust wetting‐induced climbing strategy is reported for transferring the interfacially assembled large‐area ultrathin pristine graphene film. This strategy can quickly convert solvent‐exfoliated pristine graphene dispersion into ultrathin graphene film on various substrates with different materials (glass, metal, plastics, and cloth), shapes (film, fiber, and bulk), and hydrophobic/hydrophilic patterns. It is also applicable to nanoparticles, nanofibers, and other exfoliated 2D nanomaterials for fabricating large‐area ultrathin films. Alternate climbing of different ultrathin nanomaterial films allows a layer‐by‐layer transfer, forming a well‐ordered layered composite film with the integration of multiple pristine nanomaterials at nanometer scale. This powerful strategy would greatly promote the development of solvent‐exfoliated pristine nanomaterials from dispersions to macroscopic thin film materials.     

石墨烯包覆玻璃纤维复合材料的制备及其电学性能研究

以牛血清白蛋白(BSA)改性玻璃纤维表面, 利用静电吸附原理制备氧化石墨包覆的玻璃纤维复合材料, 采用氢碘酸还原氧化石墨得到石墨烯包覆玻璃纤维导电材料。利用X射线衍射(XRD)和傅立叶变换红外光谱仪(FT-IR)等表征样品的物相结构和基团类型, 扫描电镜(SEM)表征石墨烯包覆玻璃纤维的形貌特征。当氧化石墨分散液pH低于6时, 随着pH减小, 包覆效果变得更明显。通过粒径/Zeta电位仪表征氧化石墨和BSA在不同pH下的Zeta电位, 结果表明BSA等电点约为5.3, 氧化石墨的等电点小于3。得到的石墨烯包覆玻璃纤维导电材料的电导率达到4.5 S/m, 制备的导电玻璃纤维具有一定的柔性, 在弯曲后仍能保持原有的导电性能; 导电玻璃纤维在高于100℃热处理后, 由于石墨烯在高温下可以继续还原, 其电导率得到一定的提高, 表明制备的导电玻璃纤维可以在较高温度下使用。     

Cell‐Assembled Graphene Biocomposite for Enhanced Chondrogenic Differentiation

Graphene‐based nanomaterials are increasingly being explored for use as biomaterials for drug delivery and tissue engineering applications due to their exceptional physicochemical and mechanical properties. However, the two‐dimensional nature of graphene makes it difficult to extend its applications beyond planar tissue culture. Here, graphene–cell biocomposites are used to pre‐concentrate growth factors for chondrogenic differentiation. Bone marrow‐derived mesenchymal stem cells (MSCs) are assembled with graphene flakes in the solution to form graphene‐cell biocomposites. Increasing concentrations of graphene (G) and porous graphene oxide (pGO) are found to correlate positively with the extent of differentiation. However, beyond a certain concentration, especially in the case of graphene oxide, it will lead to decreased chondrogenesis due to increased diffusional barrier and cytotoxic effects. Nevertheless, these findings indicate that both G and pGO could serve as effective pre‐concentration platforms for the construction of tissue‐engineered cartilage and suspension‐based cultures in vitro.     

Unusually High Optical Transparency in Hexagonal Nanopatterned Graphene with Enhanced Conductivity by Chemical Doping

Graphene has received appreciable attention for its potential applications in flexible conducting film due to its exceptional optical, mechanical, and electrical properties. However increasing transmittance of graphene without sacrificing the electrical conductivity has been difficult. The fabrication of optically highly transparent (≈98%) graphene layer with a reasonable electrical conductivity is demonstrated here by nanopatterning and doping. Anodized aluminium oxide nanomask prepared by facile and simple self‐assembly technique is utilized to produce an essentially hexagonally nanopatterned graphene. The electrical resistance of the graphene increases significantly by a factor of ≈15 by removal of substantial graphene regions via nanopatterning into hexagonal array pores. However, the use of chemical doping on the nanopatterned graphene almost completely recovers the lost electrical conductivity, thus leading to a desirably much more optically transparent conductor having ≈6.9 times reduced light blockage by graphene material without much loss of electrical conductivity. It is likely that the availability of large number of edges created in the nanopatterned graphene provides ideal sites for chemical dopant attachment, leading to a significant reduction of the sheet resistance. The results indicate that the nanopatterned graphene approach can be a promising route for simultaneously tuning the optical and electrical properties of graphene to make it more light‐transmissible and suitable as a flexible transparent conductor.     

Harnessing the Influence of Reactive Edges and Defects of Graphene Substrates for Achieving Complete Cycle of Room‐Temperature Molecular Sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene‐nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water‐based dispersions of single‐layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p‐type responses to NO₂ and NH₃) and the edges of graphene nanomesh structures (showing n‐type responses to NO₂ and NH₃) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene‐based materials.     

Charge Transport in Polycrystalline Graphene: Challenges and Opportunities

Graphene has attracted significant interest both for exploring fundamental science and for a wide range of technological applications. Chemical vapor deposition (CVD) is currently the only working approach to grow graphene at wafer scale, which is required for industrial applications. Unfortunately, CVD graphene is intrinsically polycrystalline, with pristine graphene grains stitched together by disordered grain boundaries, which can be either a blessing or a curse. On the one hand, grain boundaries are expected to degrade the electrical and mechanical properties of polycrystalline graphene, rendering the material undesirable for many applications. On the other hand, they exhibit an increased chemical reactivity, suggesting their potential application to sensing or as templates for synthesis of one‐dimensional materials. Therefore, it is important to gain a deeper understanding of the structure and properties of graphene grain boundaries. Here, we review experimental progress on identification and electrical and chemical characterization of graphene grain boundaries. We use numerical simulations and transport measurements to demonstrate that electrical properties and chemical modification of graphene grain boundaries are strongly correlated. This not only provides guidelines for the improvement of graphene devices, but also opens a new research area of engineering graphene grain boundaries for highly sensitive electro‐biochemical devices.     

Graphene‐Based Biosensors: Going Simple

The main properties of graphene derivatives facilitating optical and electrical biosensing platforms are discussed, along with how the integration of graphene derivatives, plastic, and paper can lead to innovative devices in order to simplify biosensing technology and manufacture easy‐to‐use, yet powerful electrical or optical biosensors. Some crucial issues to be overcome in order to bring graphene‐based biosensors to the market are also underscored.     

Vertically Aligned Graphene–Carbon Fiber Hybrid Electrodes with Superlong Cycling Stability for Flexible Supercapacitors

Graphene electrode–based supercapacitors are in high demand due to their superior electrochemical characteristics. A major bottleneck of using the supercapacitors for commercial applications lies in their inferior electrode cycle life. Herein, a simple and facile method to fabricate highly efficient supercapacitor electrodes using pristine graphene sheets vertically stacked and electrically connected to the carbon fibers which can result in vertically aligned graphene–carbon fiber nanostructure is developed. The vertically aligned graphene–carbon fiber electrode prepared by electrophoretic deposition possesses a mesoporous 3D architecture which enabled faster and efficient electrolyte‐ion diffusion with a gravimetric capacitance of 333.3 F g^?1 and an areal capacitance of 166 mF cm^?2. The electrodes displayed superlong electrochemical cycling stability of more than 100 000 cycles with 100% capacitance retention hence promising for long‐lasting supercapacitors. Apart from the electrochemical double layer charge storage, the oxygen‐containing surface moieties and α‐Ni(OH)₂ present on the graphene sheets enhance the charge storage by faradaic reactions. This enables the assembled device to provide an excellent gravimetric energy density of 76 W h kg^?1 with a 100% capacitance retention even after 1000 bending cycles. This study opens the door for developing high‐performing flexible graphene electrodes for wearable energy storage applications.     

Bioinspired Graphene‐Based Nanocomposites and Their Application in Flexible Energy Devices

Graphene is the strongest and stiffest material ever identified and the best electrical conductor known to date, making it an ideal candidate for constructing nanocomposites used in flexible energy devices. However, it remains a great challenge to assemble graphene nanosheets into macro‐sized high‐performance nanocomposites in practical applications of flexible energy devices using traditional approaches. Nacre, the gold standard for biomimicry, provides an excellent example and guideline for assembling two‐dimensional nanosheets into high‐performance nanocomposites. This review summarizes recent research on the bioinspired graphene‐based nanocomposites (BGBNs), and discusses different bioinspired assembly strategies for constructing integrated high‐strength and ‐toughness graphene‐based nanocomposites through various synergistic effects. Fundamental properties of graphene‐based nanocomposites, such as strength, toughness, and electrical conductivities, are highlighted. Applications of the BGBNs in flexible energy devices, as well as potential challenges, are addressed. Inspired from the past work done by the community a roadmap for the future of the BGBNs in flexible energy device applications is depicted.     

Ultrathin,Washable, and Large‐Area Graphene Papers for Personal Thermal Management

Freestanding, flexible/foldable, and wearable bifuctional ultrathin graphene paper for heating and cooling is fabricated as an active material in personal thermal management (PTM). The promising electrical conductivity grants the superior Joule heating for extra warmth of 42 °C using a low supply voltage around 3.2 V. Besides, based on its high out‐of‐plane thermal conductivity, the graphene paper provides passive cooling via thermal transmission from the human body to the environment within 7 s. The cooling effect of graphene paper is superior compared with that of the normal cotton fiber, and this advantage will become more prominent with the increased thickness difference. The present bifunctional graphene paper possesses high durability against bending cycles over 500 times and wash time over 1500 min, suggesting its great potential in wearable PTM.     

Clean Transfer of Large Graphene Single Crystals for High‐Intactness Suspended Membranes and Liquid Cells

The atomically thin 2D nature of suspended graphene membranes holds promising in numerous technological applications. In particular, the outstanding transparency to electron beam endows graphene membranes great potential as a candidate for specimen support of transmission electron microscopy (TEM). However, major hurdles remain to be addressed to acquire an ultraclean, high‐intactness, and defect‐free suspended graphene membrane. Here, a polymer‐free clean transfer of sub‐centimeter‐sized graphene single crystals onto TEM grids to fabricate large‐area and high‐quality suspended graphene membranes has been achieved. Through the control of interfacial force during the transfer, the intactness of large‐area graphene membranes can be as high as 95%, prominently larger than reported values in previous works. Graphene liquid cells are readily prepared by π–π stacking two clean single‐crystal graphene TEM grids, in which atomic‐scale resolution imaging and temporal evolution of colloid Au nanoparticles are recorded. This facile and scalable production of clean and high‐quality suspended graphene membrane is promising toward their wide applications for electron and optical microscopy.     

Laser‐Induced Direct Graphene Patterning and Simultaneous Transferring Method for Graphene Sensor Platform

General methods utilized in the fabrication of graphene devices involve graphene transferring and subsequent patterning of graphene via multiple wet‐chemical processes. In the present study, a laser‐induced pattern transfer (LIPT) method is proposed for the transferring and patterning of graphene in a single processing step. Via the direct graphene patterning and simultaneous transferring, the LIPT method greatly reduces the complexity of graphene fabrication while augmenting flexibility in graphene device design. Femtosecond laser ablation under ambient conditions is employed to transfer graphene/PMMA microscale patterns to arbitrary substrates, including a flexible film. Suspended cantilever structures are also demonstrated over a prefabricated trench structure via the single‐step method. The feasibility of this method for the fabrication of functional graphene devices is confirmed by measuring the electrical response of a graphene/PMMA device under laser illumination.