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The fast spread of SARS-CoV-2 has severely threatened the public health. Establishing a sensitive method for SARS-CoV-2 detection is of great significance to contain the worldwide pandemic. Here, we develop a graphene field-effect transistor (g-FET) biosensor and realize ultrasensitive SARS-CoV-2 antibody detection with a limit of detection (LoD) down to 10-18 M (equivalent to 10-16 g mL-1) level. The g-FETs are modified with spike S1 proteins, and the SARS-CoV-2 antibody biorecognition events occur in the vicinity of the graphene surface, yielding an LoD of ∼150 antibodies in 100 μL full serum, which is the lowest LoD value of antibody detection. The diagnoses time is down to 2 min for detecting clinical serum samples. As such, the g-FETs leverage rapid and precise SARS-CoV-2 screening and also hold great promise in prevention and control of other epidemic outbreaks in the future.

Direct and sensitive short-wavelength ultraviolet (UVC) dosimeters could provide a safer disinfection environment against viruses. We developed direct, quantitative, specific and highly sensitive UVC dosimeters based on DNA nanostructure-modified graphene field-effect transistors. Detectable doses of the dosimeters range from 0.005 to 6 kJ m−2 and such dosimeters have at least 5 times better sensitivity than the current direct UV dosimeters.

ConspectusSince the rise of two-dimensional (2D) materials, synthetic methods including mechanical exfoliation, solution synthesis, and chemical vapor deposition (CVD) have been developed. Mechanical exfoliation prepares randomly shaped materials with small size. Solution synthesis introduces impurities that degrade the performances. CVD is the most successful one for low-cost scalable preparation. However, when it comes to practical applications, disadvantages such as high operating temperature (∼1000 °C), probable usage of metal catalysts, contamination, defects, and interstices introduced by postgrowth transfer are not negligible. These are the reasons why plasma-enhanced CVD (PECVD), a method that enables catalyst-free in situ preparation at low temperature, is imperatively desirable.In this Account, we summarize our recent progress on controllable preparation of 2D materials by PECVD and their applications. We found that there was a competition between etching and nucleation and deposition in PECVD, making it highly controllable to obtain desired materials. Under different equilibrium states of the competition, various 2D materials with diverse morphologies and properties were prepared including pristine or nitrogen-doped graphene crystals, graphene quantum dots, graphene nanowalls, hexagonal boron nitride (h-BN), B-C-N ternary materials (BCxN), etc. We also used mild plasma to modify or treat 2D materials (e.g., WSe2) for desired properties.PECVD has advantages such as low temperature, transfer-free process, and industrial compatibility, which enable facile, scalable, and low-cost preparation of 2D materials with clean surfaces and interfaces directly on noncatalytic substrates. These merits significantly benefit the as-prepared materials in the applications. Field-effect transistors with high motilities were directly fabricated on graphene and nitrogen-doped graphene. By use of h-BN as the dielectric interfacial layer, both mobilities and saturated power densities of the devices were improved owing to the clean, closely contacted interface and enhanced interfacial thermal dissipation. High-quality materials and interfaces also enabled promising applications of these materials in photodetectors, pressure sensors, biochemical sensors, electronic skins, Raman enhancement, etc. To demonstrate the commercial applications, several prototypical devices were studied such as distributed pressure sensor arrays, touching module on a robot hand for braille recognition, and smart gloves for recording sign language. Finally, we discuss opportunities and challenges of PECVD as a comprehensive preparation methodology of 2D materials for future applications beyond traditional CVD.

Due to ultra-high reactivity, direct determination of free radicals, especially hydroxyl radical (•OH) with ultra-short lifetime, by field-effect transistor (FET) sensors remains a challenge, which hampers evaluating the role that free radical plays in physiological and pathological processes. Here, we develop a •OH FET sensor with a graphene channel functionalized by metal ion indicators. At the electrolyte/graphene interface, highly reactive •OH cuts the cysteamine to release the metal ions, resulting in surface charge de-doping and a current response. By this inner-cutting strategy, the •OH is selectively detected with a concentration down to 10−9 M. Quantitative metal ion doping enables modulation of the device sensitivity and a quasi-quantitative detection of •OH generated in aqueous solution or from living cells. Owing to its high sensitivity, selectivity, real-time label-free response, capability for quasi-quantitative detection and user-friendly portable feature, it is valuable in biological research, human health, environmental monitoring, etc., Field effect transistors based on graphene hold promise for future sensing applications. Here, the authors report a free radical sensor in which the •OH radical cuts cysteamine to release Cd2+ from the electrolyte/graphene interface and selectively detects •OH with a concentration down to 10−9 M.

Silicon-based Schottky heterojunction photodetectors are promising due to their compatibility with the semiconductor process. However, the applications of these devices are usually limited to wavelengths shorter than 1.1 µm due to the low absorption of electrode materials at infrared. In this report, silicon-based compound semiconductor heterojunction photodetectors with graphene transparent electrodes are fabricated. Due to the high absorption of InSb at infrared, as well as the good transparency and excellent electrical conductivity of the graphene, the as-prepared photodetectors show a broadband photoresponse with high performance which includes a specific detectivity of 1.9 [Formula: see text]1012 cm Hz1/2 W-1, responsivity of 132 mA W-1, on/off ratio of 1 [Formula: see text]105, rise time of 2 µs, 3 dB cut-off frequency of 172 kHz, and response wavelengths covering 635 nm, 1.55 µm and 2.7 µm. This report proves that graphene as a transparent electrode has a great effect on the performance improvement of silicon-based compound semiconductor heterojunction photodetectors.

Three-dimensional (3D) graphene foam (GF) produced by template-directed chemical vapour deposition (CVD) has shown great potential for applications in composite phase change materials (PCMs) with enhanced thermal conductivity and graphene aerogel (GA) has been proved to be effective supporting scaffold to improve the shape-stability of organic PCMs. Here, hybrid graphene aerogel (HGA) is encapsulated in GF framework to obtain a 3D GF/HGA (GH) hybrid microstructure via combined self-assembly and CVD techniques. The thermal conductivity of paraffin wax (PW)/GH composite PCMs increases by 574% and 98% compared with pure PW and PW/GF composite PCMs, respectively. Meanwhile, PW/GH composite PCM exhibits better shape stability than PW/GF composite PCM, high thermal energy storage density, good thermal reliability and chemical stability. PW/GH composite PCMs also realize efficient light-to-thermal energy conversion and storage owing to the excellent photoabsorption. This study sheds light on the development of the composite PCMs with good comprehensive properties, which are potentially to be used widely in energy storage systems.

Graphene has been highly sought after as a potential candidate for hot-electron terahertz (THz) detection benefiting from its strong photon absorption, fast carrier relaxation, and weak electron-phonon coupling. Nevertheless, to date, graphene-based thermoelectric THz photodetection is hindered by low responsivity owing to relatively low photoelectric efficiency. In this work, we provide a straightforward strategy for enhanced THz detection based on antenna-coupled CVD graphene transistors with the introduction of symmetric paired fingers. This design enables switchable photodetection modes by controlling the interaction between the THz field and free hot carriers in the graphene-channel through different contacting configurations. Hence a novel “bias-field effect” can be activated, which leads to a drastic enhancement in THz detection ability with maximum responsivity of up to 280 V/W at 0.12 THz relative to the antenna area and a Johnson-noise limited minimum noise-equivalent power (NEP) of 100 pW/Hz0.5 at room temperature. The mechanism responsible for the enhancement in the photoelectric gain is attributed to thermophotovoltaic instead of plasma self-mixing effects. Our results offer a promising alternative route toward scalable, wafer-level production of high-performance graphene detectors. Controlling how finger-like electrodes are positioned on graphene transistors makes it simpler to detect terahertz radiation for applications including medical diagnostics. When photons strike graphene sheets, multiple electrons with high kinetic energy are released. Changlong Liu at the Chinese Academy of Sciences, Shanghai, and coworkers have exploited these electrons to improve detection of terahertz light, which is useful for seeing features underneath human skin. The team’s device places single-layer graphene into a channel flanked by two microscale antennas, and then adds a pair of thin metal fingers on top of the 2D carbon film. By manipulating the separation of the finger contacts, the team unlocked an enhanced response to terahertz light at room temperature. Experiments and simulations revealed that temperature gradients between contact points generated a terahertz-sensitive photocurrent through conversion of heat into electricity. Graphene is very promising for THz application, especially in the fields desiring fast THz imaging, like security screening, communication, biomedical and pharmacy control. However, current graphene-based THz detectors are severely hindered by its poor switching behavior, and lack of internal gain to boost up the responsivity in the framework of plasma-wave self-mixing or thermoelectric detections. A proper means to selectively trigger the photoelectric conversion is highly desirable for practical applications. This work offers alternative way for room temperature THz detection via manipulating the hot carriers either electrically and electromagnetically. Internal photoelectric gain is achieved via the bias-field effect, which leads to the giant enhancement of graphene-based detector’s responsivity over 200 V/W. Furthermore, switching behavior between photoconductive and photovoltaic modes can be given rise in a single device, being promising for scalable THz imaging.

Flexible pressure sensors have attracted a lot of interest because of their widespread applications in healthcare, robotics, wearable smart devices, and human-machine interfaces. While microstructuring both the electrodes and dielectrics has been proven to have a significant improvement in the sensitivity and response speed of piezocapacitive sensors, the synergetic influence of microstructured electrodes and dielectrics has not been discussed yet. Herein, a flexible piezocapacitive sensor has been demonstrated with a microstructured graphene nanowalls (GNWs) electrode and a conformally microstructured dielectric layer that consists of polydimethylsiloxane (PDMS) and piezoelectric enhancer of zinc oxide (ZnO). Such microstructured assembly with piezoelectric film constructs a microconformal GNWs/PDMS/ZnO electrode-dielectric integration (MEDI), which can effectively enhance the sensitivity and the pressure-response range. The piezocapacitive sensor exhibits an ultra-high sensitivity (22.3 kPa−1), fast response speed (25 ms), and broad pressure range (22 kPa). The finite element analysis indicates that the polarized electric field caused by the ZnO film’s piezoelectric effect greatly enhances the capacitance of the sensor. Moreover, the integration of the electrode and dielectric layer can eliminate the slippage between contiguous layers, which effectively increases the mechanical stability. Benefitting from the outstanding comprehensive performance, the potential application in robotic tactile perception has been successfully demonstrated, including object grabbing, braille recognition, and roughness detection. The MEDI in structure capacitive sensors provides a new approach to achieve high-performance E-skin, which delivers great potential applications in next-generation robotic tactile sensing.

Three-dimensional (3D) graphene has attracted increasing attention in electrochemical devices. However, the existing preparation technologies usually involve a solvent process, which introduces defects and functional groups into the 3D network. Here, we find the defects and functional groups influence the electrochemical stability of graphene. After an electrochemical process, the current decreases by more than 1 order of magnitude, indicating remarkable etching of graphene. To improve the electrochemical stability, we develop a solvent-free preparation process to produce 3D graphene for the first time. After growth on a 3D microporous copper by chemical vapor deposition (CVD), the copper template is removed by a high temperature evaporation process, resulting in 3D graphene network without any solvent process involved. The samples exhibit remarkably improved stability with durable time 2 times, compared with normal CVD samples, and 55 times, compared with reduced graphite oxide, and no obvious etching is...

Recently, graphene foam (GF) with a three-dimensional (3D) interconnected network produced by template-directed chemical vapor deposition (CVD) has been used to prepare composite phase-change materials (PCMs) with enhanced thermal conductivity. However, the pore size of GF is as large as hundreds of micrometers, resulting in a remarkable thermal resistance for heat transfer from the PCM inside the large pores to the GF strut walls. In this study, a novel 3D hierarchical GF (HGF) is obtained by filling the pores of GF with hollow graphene networks. The HGF is then used to prepare a paraffin wax (PW)-based composite PCM. The thermal conductivity of the PW/HGF composite PCM is 87% and 744% higher than that of the PW/GF composite PCM and pure PW, respectively. The PW/HGF composite PCM also exhibits better shape stability than the PW/GF composite PCM, negligible change in the phase-change temperature, a high thermal energy storage density that is 95% of pure PW, good thermal reliability, and chemical stability with cycling for 100 times. More importantly, PW/HGF composite PCM allows light-driven thermal energy storage with a high light-to-thermal energy conversion and storage efficiency, indicating its great potential for applications in solar-energy utilization and storage.

Conjugated microporous polymers (CMPs) have attracted intensive attention owing to their permanent nanoporosity, large surface area and possibility for functionalization, however their application in energy storage suffers from poor conductivity and low hetero-atom content. Here, we demonstrate a hybrid of conjugated microporous polymers and graphene aerogel with improved conductivity. After treating at 800°C in NH3, the nitrogen content increases to 9.8%. The resulting microporous carbon exhibits a significant rise in supercapacitive performance up to 325 F g−1, 55% higher than pristine triazine-based CMPs, with energy density up to 12.95 Wh kg−1. Moreover, it has high stability with 99% retention after 10,000 cycles at 5 A g−1. The synergy of hierarchical porous structure, graphene-based conduction path and high percentage of hybridization with nitrogen ensures effective ion/electron transport and diffusion, making NH3-treated graphene aerogel/CMP hybrid a promising electrode material in high-performance supercapacitor.

Conformal graphene films have directly been synthesized on the surface of grating microstructured quartz substrates by a simple chemical vapor deposition process. The wonderful conformality and relatively high quality of the as-prepared graphene on the three-dimensional substrate have been verified by scanning electron microscopy and Raman spectra. This conformal graphene film possesses excellent electrical and optical properties with a sheet resistance of2000 Ω·sq(-1) and a transmittance of80% (at 550 nm), which can be attached with a flat graphene film on a poly(dimethylsiloxane) substrate, and then could work as a pressure-sensitive sensor. This device possesses a high-pressure sensitivity of -6.524 kPa(-1) in a low-pressure range of 0-200 Pa. Meanwhile, this pressure-sensitive sensor exhibits super-reliability (≥5000 cycles) and an ultrafast response time (≤4 ms). Owing to these features, this pressure-sensitive sensor based on 3D conformal graphene is adequately introduced to test wind pressure, expressing higher accuracy and a lower background noise level than a market anemometer.

High-performance infrared (IR) photodetectors made by low dimensional materials promise a wide range of applications in communication, security and biomedicine. Moreover, light-harvesting effects based on novel plasmonic materials and their combinations with two-dimensional (2D) materials have raised tremendous interest in recent years, as they may potentially help the device complement or surpass currently commercialized IR photodetectors. Graphene is a particularly attractive plasmonic material because graphene plasmons are electrically tunable with a high degree of electromagnetic confinement in the mid-infrared (mid-IR) to terahertz regime and the field concentration can be further enhanced by forming nanostructures. Here, we report an efficient mid-IR room-temperature photodetector enhanced by plasmonic effect in graphene nanoresonators (GNRs)/graphene heterostructure. The plasmon polaritons in GNRs are size-dependent with strong field localization. Considering that the size and density of GNRs are controllable by chemical vapor deposition method, our work opens a cost-effective and scalable pathway to fabricate efficient IR optoelectronic devices with wavelength tunability.

Graphene is regarded as a potential surface-enhanced Raman spectroscopy (SERS) substrate. However, the application of graphene quantum dots (GQDs) has had limited success due to material quality. Here, we develop a quasi-equilibrium plasma-enhanced chemical vapor deposition method to produce high-quality ultra-clean GQDs with sizes down to 2 nm directly on SiO2/Si, which are used as SERS substrates. The enhancement factor, which depends on the GQD size, is higher than conventional graphene sheets with sensitivity down to 1 × 10−9 mol L−1 rhodamine. This is attributed to the high-quality GQDs with atomically clean surfaces and large number of edges, as well as the enhanced charge transfer between molecules and GQDs with appropriate diameters due to the existence of Van Hove singularities in the electronic density of states. This work demonstrates a sensitive SERS substrate, and is valuable for applications of GQDs in graphene-based photonics and optoelectronics., Surface-enhanced Raman spectroscopy (SERS) is a promising technology for sensitive optical sensors, generally using rough metal films. Here, Liu et al. synthesize high-quality graphene quantum dot films which offer a large SERS enhancement due to a strong light-matter interaction with Van Hove singularities.

Photodetectors exploiting photoejected hot electrons have the potential to achieve ultrahigh sensitivity and broadband detection capabilities, which are controlled by the structure of the device rather than the bandgap of the employed materials. However, the achievement of photodetectors of long-wavelength photons with both high responsivity and bandwidth is still challenging. Here, a novel class of high-gain photodetectors based on the manipulation of intrinsic hot carriers by exploiting the electromagnetic engineering of a graphene-based active channel is presented. Light field is focused in a split-finger gated structure to create a potential gradient in the channel, which is able to trap and detrap the charges laterally transferred from low resistive Au-graphene interface, finally leading to a high photoconductive gain. Correspondingly, the device activity can be easily switched from photovoltaic to photoconductive, depending on the photoinduced hot-carrier distribution, just by controlling the electric field. The device shows tunable sensitivity, higher energy efficiency, and photoconductive gain. In particular, the responsivity (0.6-6.0 kV W-1) and the noise-equivalent power (less than 0.1 nW Hz-0.5 at room temperature) are significantly improved even at low-energy terahertz band with respect to state-of-the-art devices based on extrinsically coupled hot carriers operating in the near infrared. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Nitrogen doping is one of the most promising routes to modulate the electronic characteristic of graphene. Plasma-enhanced chemical vapor deposition (PECVD) enables low-temperature graphene growth. However, PECVD growth of nitrogen doped graphene (NG) usually requires metal-catalysts, and to the best of our knowledge, only amorphous carbon-nitrogen films have been produced on dielectric surfaces by metal-free PECVD. Here, a critical factor for metal-free PECVD growth of NG is reported, which allows high quality NG crystals to be grown directly on dielectrics like SiO2/Si, Al2O3, h-BN, mica at 435 °C without a catalyst. Thus, the processes needed for loading the samples on dielectrics and n-type doping are realized in a simple PECVD, which would be of significance for future graphene electronics due to its compatibility with the current microelectronic processes.

Graphene has attracted tremendous research interest owing to its widespread potential applications. However, these applications are partially hampered by the lack of a general method to produce high-quality graphene at low cost. Here, to the best of our knowledge, we use low-cost solid carbon allotropes as the precursor in plasma-enhanced chemical vapor deposition (PECVD) for the first time, and find that the hydrogen plasma and reaction temperature play a crucial role in the process. Hydrogen plasma etches carbon black, and produces graphene crystals in a high-temperature zone. Based on this finding, a modified PECVD technology is developed, which produces transparent conductive nanographene films directly on various substrates at a temperature as low as 600 °C. For application, the closely packed structure of the nanographene film enables a remarkable temperature-dependent behavior of the resistance with a ratio higher than that previously reported, indicating its great potential for usage in highly sensitive temperature detectors.

Graphene and its derivatives hold a great promise for widespread applications such as field-effect transistors, photovoltaic devices, supercapacitors, and sensors due to excellent properties as well as its atomically thin, transparent, and flexible structure. In order to realize the practical applications, graphene needs to be synthesized in a low-cost, scalable, and controllable manner. Plasma-enhanced chemical vapor deposition (PECVD) is a low-temperature, controllable, and catalyst-free synthesis method suitable for graphene growth and has recently received more attentions. This review summarizes recent advances in the PECVD growth of graphene on different substrates, discusses the growth mechanism and its related applications. Furthermore, the challenges and future development in this field are also discussed.

Because of its atomic thickness, excellent properties, and widespread applications, graphene is regarded as one of the most promising candidate materials for nanoelectronics. The wider use of graphene will require processes that produce this material in a controllable manner. In this Account, we focus on our recent studies of the controllable chemical vapor deposition (CVD) growth of graphene, especially few-layer graphene (FLG), and the applications of this material in electronic devices. CVD provides various means of control over the morphologies of the produced graph ene. We studied several variables that can affect the CVD growth of graphene, including the catalyst, gas flow rate, growth time, and growth temperature and successfully achieved the controlled growth of hexagonal graphene crystals. Moreover, we developed several modified CVD methods for the controlled growth of FLGs. Patterned CVD produced FLGs with desired shapes in required areas. By introducing dopant precursor in the CVD process, we produced substitutionally doped FLGs, avoiding the typically complicated post-treatment processes for graphene doping. We developed a template CVD method to produce FLG ribbons with controllable morphologies on a large scale. An oxidation-activated surface facilitated the CVD growth of polycrystalline graphene without the use of a metal catalyst or a complicated postgrowth transfer process. In devices, CVD offers a controllable means to modulate the electronic properties of the graphene samples and to improve device performance. Using CVD-grown hexagonal graphene crystals as the channel materials in field-effect transistors (FETs), we improved carrier mobility. Substitutional doping of graphene in CVD opened a band gap for efficient FET operation and modulated the Fermi energy level for n-type or p-type features. The similarity between the chemical structure of graphene and organic semiconductors suggests potential applications of graphene in organic devices. We used patterned CVD FLGs as the bottom electrodes in pentacene FETs. The strong π-π interactions between graphene and pentacene produced an excellent interface with low contact resistance and a reduced injection barrier, which dramatically enhances the device performance. We also fabricated reversible nanoelectromechanical (NEM) switches and a logic gate using the FLG ribbons produced using our template CVD method. In summary, CVD provides a controllable means to produce graphene samples with both large area and high quality. We developed several modified CVD methods to produce FLG samples with controlled shape, location, edge, layer, dopant, and growth substrate. As a result, we can modulate the properties of FLGs, which provides materials that could be used in FETs, OFETs, and NEM devices. Despite remarkable advances in this field, further exploration is required to produce consistent, homogeneous graphene samples with single layer, single crystal, and large area for graphene-based electronics.

Graphene, a two-dimensional material, is regarded as one of the most promising candidates for future nanoelectronics due to its atomic thickness, excellent properties and widespread applications. As the first step to investigate its properties and finally to realize the practical applications, graphene must be synthesized in a controllable manner. Thus, controllable synthesis is of great significance, and received more and more attention recently. This Progress Report highlights recent advances in controllable synthesis of graphene, clarifies the problems, and prospects the future development in this field. The applications of the controllable synthesis are also discussed.

Metal-catalyzed chemical vapor deposition (CVD) has been broadly employed for large-scale production of high-quality graphene. However, a following transfer process to targeted substrates is needed, which is incompatible with current silicon technology. We here report a new CVD approach to form nanographene and nanographite films with accurate thickness control directly on non-catalytic substrates such as silicon dioxide and quartz at 800 °C. The growth time is as short as a few seconds. The approach includes using 9-bis(diethylamino)silylanthracene as the carbon source and an atomic layer deposition (ALD) controlling system. The structure of the formed nanographene and nanographite films were characterized using atomic force microscopy, high resolution transmission electron microscopy, Raman scattering, and x-ray photoemission spectroscopy. The nanographite film exhibits a transmittance higher than 80% at 550 nm and a sheet electrical resistance of 2000 ohms per square at room temperature. A negative temperature-dependence of the resistance of the nanographite film is also observed. Moreover, the thickness of the films can be precisely controlled via the deposition cycles using an ALD system, which promotes great application potential for optoelectronic and thermoelectronic-devices.

Controllable and scalable production is of great importance for the application of graphene; however, to date, it is still a great challenge and a major obstacle which hampers its practical applications. Here, we develop a template chemical vapor deposition method for scalable synthesis of few-layer graphene ribbons (FLGRs) with controlled morphologies. The FLGRs have a good conductivity and are ideal for use in nanoelectromechanics (NEM). As an application, we fabricate a reversible NEM switch and a logic gate by using the FLGRs. This work realizes both controllable and scalable synthesis of graphene, provides an application of graphene in NEM switches, and would be valuable for both the scientific studies and the practical applications of graphene.

A simple and effective air-annealing technique was developed to stably improve both the electrical conductivity and light transmission of pristine graphene. After the graphene film was annealed in air at 250 °C for 80 min, the mobility and carrier concentration were both significantly enhanced, and the sheet resistance was greatly reduced with a decrease rate of ~33%. Meanwhile, the transparency was also improved by more than 3%. The mechanism is carefully discussed. The reason might be that air-annealing conditions provide a suitable atmosphere to etch and remove amorphous carbons. More importantly, the enhanced transparent conductive properties of the air-annealed graphene films were extraordinarily stable, and remained almost unchanged for 100 days.

Graphene is regarded as one of the most promising candidate materials for future electronics. For usage in electrical devices, high-quality graphene needs to be placed on a dielectric surface. Currently, methods for graphene preparation require graphene to be transferred from scotch tape, metals, or solutions to the dielectric substrate for electrical applications. The transfer process normally induces contamination, wrinkles, or even breakage of the graphene samples and thus hampers the practical application of graphene in electronics. Moreover, chemical vapor deposition (CVD) on a metal catalyst normally requires a growth temperature as high as 800–1000 8C. For industrial-scale production, lowtemperature growth can lead to a decrease in energy consumption and cost, and an increase in compatibility. Therefore, a low-cost, controllable, and reliable method is required for the production of clean high-quality graphene directly on dielectric substrates at low temperature. One pioneering study towards the goal of the catalyst-free growth of graphene on dielectric materials examined the pyrolysis of CH4 on bare SiO2/Si; [5,6] however, this method requires a high growth temperature (1100–1650 8C). Another approach, plasma-enhanced CVD (PECVD), enables the low-temperature growth of graphene on metals, or even on dielectric surfaces (550–650 8C). However, without metal catalysts, structural defects readily form at the edges and terminate graphene growth. As a result, small graphene nanoclusters or noncrystalline samples are formed, the quality of which is lower than that required for electrical applications. Vertically oriented graphene nanosheets can be produced by PECVD; however, most of the products are multilayered. Herein, we describe the development of a critical PECVD (c-PECVD) growth method, in which a H2 plasma is introduced during graphene growth. H2 plasma is known to etch graphene from the edges. Moderate etching by a H2 plasma removes defects generated at the edges and thus keeps the edges atomically smooth and active during the whole process of graphene crystal growth. Therefore, in a critical equilibrium state between H2 plasma etching and CH4 or C2H4 plasma growth, we observed efficient catalyst-free crystal growth of graphene directly on crystalline sapphire, highly oriented pyrolytic graphite (HOPG), and the amorphous surface of Si substrates with a thermally grown 300 nm SiO2 overlayer (SiO2/Si), with crystal sizes up to the micrometer scale for single-layer hexagonal single crystals and up to the centimeter scale for continuous films. The growth temperature could be decreased to as low as 400 8C when C2H4 was used as the carbon source. To the best of our knowledge, this temperature is one of the lowest used for the catalyst-free growth of graphene. In the experiments, a homemade remote radiofrequency (13.56 mHz) PECVD system (80 W) was used (Figure 1a). Figure 1b illustrates the typical procedure for the c-PECVD growth of graphene on bare Si/SiO2 (see the Experimental Section for details). We first used peel-off graphene to clarify the etching, critical edge growth, and nucleation of graphene in PECVD. Figure 1c shows atomic force microscopy (AFM) images of a trilayer peel-off graphene flake before and after cPECVD growth (H2 plasma activation: 250 mTorr, 500 8C; growth: 30% H2, 90 mTorr, 600 8C, 60 min). The edges of the bottom, middle, and upper layer moved by 79, 117, and 158 nm, respectively, thus indicating that continuous growth of the flake took place on the edges, rather than in the plane. The different growth rate of each layer is attributed to the substrate (see Figure S1 in the Supporting Information). Control experiments show that the edge growth is highly dependent on the H2 content, the growth temperature, and the pressure (Figure 1d). Lower temperatures or higher H2 content tend to induce edge etching, whereas the opposite reaction conditions cause the nucleation of graphitic clusters (see Figure S2). For example, after CH4+H2 plasma CVD at a lower temperature (550 8C), instead of growth, the edges of the flakes were etched by about 168 nm (Figure 1e). Upon CH4+H2 plasma CVD at a lower H2 content (20%), besides the edge growth, small graphitic clusters were nucleated on whole surface of the graphene flakes and SiO2/Si surface with heights lower than 1 nm (Figure 1 f); the heights observed indicate the single-layered nature of the nucleated clusters. The edge growth (Figure 1c; see also Figure S3) only takes place at a well-controlled critical temperature between those needed for nucleation and edge etching, and the critical temperature decreases as the H2 content decreases (Figure 1d). When C2H4 was used as the carbon source in cPECVD (0%H2, 48 mTorr), the critical temperature for edge growth decreased to as low as 400 8C (Figure 1d). Moreover, low pressure can lead to a remarkable improvement in the growth rate. The growth rate (30% H2, 600 8C) was about [*] Dr. D. Wei, Dr. Y. Lu, Prof. W. Chen, Prof. A. T. S. Wee Department of Physics, National University of Singapore 2 Science Drive 3, Singapore 117542 (Singapore) E-mail: phyweid@nus.edu.sg phyweets@nus.edu.sg

We report significant changes of optical conductivity (${\ensuremath{\sigma}}_{1}$) in single-layer graphene induced by mild oxygen plasma exposure and explore the interplay between carrier doping, disorder, and many-body interactions from their signatures in the absorption spectrum. The first distinctive effect is the reduction of the excitonic binding energy that can be extracted from the renormalized saddle point resonance at 4.64 eV. Secondly, ${\ensuremath{\sigma}}_{1}$ is nearly completely suppressed (${\ensuremath{\sigma}}_{1}\ensuremath{\ll}{\ensuremath{\sigma}}_{0}$) below an exposure-dependent threshold in the near-infrared range. The clear steplike suppression follows the Pauli blocking behavior expected for doped monolayer graphene. The nearly zero residual conductivity below \ensuremath{\omega} \ensuremath{\sim} 2${E}_{F}$ can be interpreted as arising from the weakening of the electronic self-energy. Our data shows that mild oxygen exposure can be used to controllably dope graphene without introducing the strong physical and chemical changes that are common in other approaches to oxidized graphene, allowing a controllable manipulation of the optical properties of graphene.

Graphene is often regarded as one of the most promising candidates for future nanoelectronics. As an indispensable component in graphene-based electronics, the formation of junctions with other materials not only provides utility functions and reliable connexions, but can also improve or alter the properties of pristine graphene, opening up possibilities for new applications. Here we demonstrate an intramolecular junction produced by the controllable unzipping of single-walled carbon nanotubes, which combines a graphene nanoribbon and single-walled carbon nanotube in a one-dimensional nanostructure. This junction shows a strong gate-dependent rectifying behaviour. As applications, we demonstrate the use of the junction in prototype directionally dependent field-effect transistors, logic gates and high-performance photodetectors, indicating its potential in future graphene-based electronics and optoelectronics.

Graphene has attracted much interest in both academia and industry. The challenge of making it semiconducting is crucial for applications in electronic devices. A promising approach is to reduce its physical size down to the nanometer scale. Here, we present the surface-assisted bottom-up fabrication of atomically precise armchair graphene nanoribbons (AGNRs) with predefined widths, namely 7-, 14- and 21-AGNRs, on Ag(111) as well as their spatially resolved width-dependent electronic structures. STM/STS measurements reveal their associated electron scattering patterns and the energy gaps over 1 eV. The mechanism to form such AGNRs is addressed based on the observed intermediate products. Our results provide new insights into the local properties of AGNRs, and have implications for the understanding of their electrical properties and potential applications.

To realize graphene-based electronics, various types of graphene are required; thus, modulation of its electrical properties is of great importance. Theoretic studies show that intentional doping is a promising route for this goal, and the doped graphene might promise fascinating properties and widespread applications. However, there is no experimental example and electrical testing of the substitutionally doped graphene up to date. Here, we synthesize the N-doped graphene by a chemical vapor deposition (CVD) method. We find that most of them are few-layer graphene, although single-layer graphene can be occasionally detected. As doping accompanies with the recombination of carbon atoms into graphene in the CVD process, N atoms can be substitutionally doped into the graphene lattice, which is hard to realize by other synthetic methods. Electrical measurements show that the N-doped graphene exhibits an n-type behavior, indicating substitutional doping can effectively modulate the electrical properties of graphene. Our finding provides a new experimental instance of graphene and would promote the research and applications of graphene.