In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO2) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO2 nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g−1, areal capacitance: 1.11 F cm−2) which leads to an exceptionally high energy density of 39.28 Wh kg−1 and power density of 128.01 kW kg−1. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.
Active nanophotonic devices are attractive due to their low-power consumption, ultrafast modulation speed and high-density integration. Although electrical operation is required for practical implementation of these devices, it is not straightforward to introduce a proper current path into such a wavelength-scale nanostructure without affecting the optical properties. For example, to demonstrate electrically driven nanolasers, complicated fabrication techniques have been used thus far. Here we report an electrically driven microdisk laser using a transparent graphene electrode. Current is injected efficiently through the graphene sheet covering the top surface of the microdisk cavity, and, for the first time, lasing operation was achieved with a low-threshold current of ~300 μA at room temperature. In addition, we measured significant electroluminescence from a graphene-contact subwavelength-scale single nanopillar structure. This work represents a new paradigm for the practical applications of integrated photonic systems, by conformally mounting graphene on the complex surfaces of non-planar three-dimensional nanostructures.
Microdisk lasers are useful for compact wavelength-scale photonic devices and circuits, but their operation by electrical injection can hamper their optical properties. Kim et al. show that a graphene-contact electrode provides efficient electrical injection while minimising optical losses.
Here we report on a scalable and direct growth of graphene micro ribbons on SiO2 dielectric substrates using a low temperature chemical vapor deposition. Due to the fast annealing at low temperature and dewetting of Ni, continuous few-layer graphene micro ribbons grow directly on bare dielectric substrates through Ni assisted catalytic decomposition of hydrocarbon precursors. These high quality graphene micro ribbons exhibit low sheet resistance of ~700 Ω −2100 Ω, high on/off current ratio of ~3, and high carrier mobility of ~655 cm2V−1s−1 at room temperature, all of which have shown significant improvement over other lithography patterned CVD graphene micro ribbons. This direct approach can in principle form graphene ribbons of any arbitrary sizes and geometries. It allows for a feasible methodology towards better integration with semiconductor materials for interconnect electronics and scalable production for graphene based electronic and optoelectronic applications where the electrical gating is the key enabling factor.
A sensitive and selective field-effect transistor (FET) biosensor is demonstrated using vertically-oriented graphene (VG) sheets labeled with gold nanoparticle (NP)-antibody conjugates. VG sheets are directly grown on the sensor electrode using a plasma-enhanced chemical vapor deposition (PECVD) method and function as the sensing channel. The protein detection is accomplished through measuring changes in the electrical signal from the FET sensor upon the antibody-antigen binding. The novel biosensor with unique graphene morphology shows high sensitivity (down to ~2 ng/ml or 13 pM) and selectivity towards specific proteins. The PECVD growth of VG presents a one-step and reliable approach to prepare graphene-based electronic biosensors.
Graphene has significant potential for application in electronics1-5, but cannot be used for effective field-effect transistors operating at room temperature because it is a semimetal with a zero bandgap6,7. Processing graphene sheets into nanoribbons with widths of less than 10nm can open up a bandgap that is large enough for room temperature transistor operation8-19, but nanoribbon devices often have low driving currents or transconductances18,19. Moreover, practical devices and circuits will require the production of dense arrays of ordered nanoribbons, which is of significant challenge20,21. Here we report the production of a new graphene nanostructure - which we call graphene nanomesh - that can open up a band gap in a large sheet of graphene to create a semiconducting thin film. The nanomeshes are prepared with block copolymer lithography and can have variable periodicities and neck widths down to 5 nm. Graphene nanomesh field-effect transistors can support currents nearly 100 times greater than individual graphene nanoribbon devices, and the on-off ratio - which is comparable with the values achieved in individual nanoribbon devices - can be tuned by varying the neck width. The block copolymer lithography approach used to make the nanomesh devices is intrinsically scalable and could allow for the rational design and fabrication of graphene-based devices and circuits with standard semiconductor processing.
The chemical stability of graphene and other free-standing two-dimensional crystals means that they can be stacked in different combinations to produce a new class of functional materials, designed for specific device applications. Here we report resonant tunnelling of Dirac fermions through a boron nitride barrier, a few atomic layers thick, sandwiched between two graphene electrodes. The resonance occurs when the electronic spectra of the two electrodes are aligned. The resulting negative differential conductance in the device characteristics persists up to room temperature and is gate voltage-tuneable due to graphene’s unique Dirac-like spectrum. Although conventional resonant tunnelling devices comprising a quantum well sandwiched between two tunnel barriers are tens of nanometres thick, the tunnelling carriers in our devices cross only a few atomic layers, offering the prospect of ultra-fast transit times. This feature, combined with the multi-valued form of the device characteristics, has potential for applications in high-frequency and logic devices.
Multilayer stacks of graphene and related two-dimensional crystals can be tailored to create new classes of functional materials. Britnell et al. report resonant tunnelling of Dirac fermions and tunable negative differential conductance in a graphene-boron nitride-graphene transistor.
Graphene has recently become a unique playground for studying light-matter interaction effects in low-dimensional electronic systems. Being of strong fundamental importance, these effects also open a wide range of opportunities in photonics and optoelectronics. In particular, strong and broadband light absorption in graphene allows one to achieve high carrier densities essential for observation of nonlinear optical phenomena. Here, we make use of strong photon-drag effect to generate and optically manipulate ultrafast photocurrents in graphene at room temperature. In contrast to the recent reports on injection of photocurrents in graphene due to external or built-in electric field effects and by quantum interference, we force the massless charge carriers to move via direct transfer of linear momentum from photons of incident laser beam to excited electrons in unbiased sample. Direction and amplitude of the drag-current induced in graphene are determined by polarization, incidence angle and intensity of the obliquely incident laser beam. We also demonstrate that the irradiation of graphene with two laser beams of the same wavelength offers an opportunity to manipulate the photocurrents in time domain. The obtained all-optical control of the photocurrents opens new routes towards graphene based high-speed and broadband optoelectronic devices.
We report the development of a multilayered graphene-Al2O3 nanopore platform for the sensitive detection of DNA and DNA-protein complexes. Graphene-Al2O3 nanolaminate membranes are formed by sequentially depositing layers of graphene and Al2O3 with nanopores being formed in these membranes using an electron-beam sculpting process. The resulting nanopores are highly robust, exhibit low electrical noise (significantly lower than nanopores in pure graphene), are highly sensitive to electrolyte pH at low KCl concentrations (attributed to the high buffer capacity of Al2O3) and permit the electrical biasing of the embedded graphene electrode, thereby allowing for three terminal nanopore measurements. In proof-of-principle biomolecule sensing experiments, the folded and unfolded transport of single DNA molecules and RecA coated DNA complexes could be discerned with high temporal resolution. The process described here also enables nanopore integration with new graphene based structures, including nanoribbons and nanogaps, for single molecule DNA sequencing and medical diagnostic applications.
Nanopore; graphene; DNA; translocation; sequencing
Graphene is now the most attractive carbon-based material. Integration of 2D graphene sheets into macroscopic architectures such as fibers illuminates the direction to translate the excellent properties of individual graphene into advanced hierarchical ensembles for promising applications in new graphene-based nanodevices. However, the lack of effective, low-cost and convenient assembly strategy has blocked its further development. Herein, we demonstrate that neat and macroscopic graphene fibers with high mechanical strength and electrical conductivity can be fluidly spun from the common graphene oxide (GO) suspensions in large scale followed with chemical reduction. The curliness-fold formation mechanism of GO fiber has been proposed. This wet-spinning technique presented here facilitates the multifunctionalization of macroscopic graphene-based fibers with various organic or inorganic components by an easy-handle in situ or post-synthesis approach, which builds the solid foundation to access a new family of advanced composite materials for the next practical applications.
Due to fascinating electronic properties and great potential in various applications, graphene has attracted great interest. Recently, much work have focused on the synthesis of different sizes and properties of graphene or graphene oxides (GOs), for example, graphene nanoribbons, nanosized graphene pieces, and nanosized triangular and hexagonal graphene sheets terminated by zigzag edges. Herein, we have demonstrated a widely available approach to fabricate the nanoscale GO pieces by directly solution-phase cutting a large-area GO sheet into nanoscale pieces via spontaneous redox reactions at room temperature. In this process, GO acts with dual functions as a model and a reducing reagent. With a typical example of silver ions, we have investigated in detail the influence of the reaction time and concentration of metal ions on yield and size of nanoscale GO pieces. Moreover, we also obtain Ag nanoparticle coating on the GO surface. Finally, a possible mechanism is suggested to explain the formation of nanoscale GO pieces.
Graphene oxides; Nanoscale graphene oxide pieces; Spontaneous redox reaction; Metal particles
Graphene exhibits exciting properties which make it an appealing candidate for use in electronic devices. Reliable processes for device fabrication are crucial prerequisites for this. We developed a large area of CVD synthesis and transfer of graphene films. With patterning of these graphene layers using standard photoresist masks, we are able to produce arrays of gated graphene devices with four point contacts. The etching and lift off process poses problems because of delamination and contamination due to polymer residues when using standard resists. We introduce a metal etch mask which minimises these problems. The high quality of graphene is shown by Raman and XPS spectroscopy as well as electrical measurements. The process is of high value for applications, as it improves the processability of graphene using high-throughput lithography and etching techniques.
We report a simple method to fabricate macroscopic, 3-D, free standing, all-carbon scaffolds (porous structures) using multiwalled carbon nanotubes (MWCNTs) as the starting materials. The scaffolds prepared by radical initiated thermal crosslinking, and annealing of MWCNTs possess macroscale interconnected pores, robust structural integrity, stability, and conductivity. The porosity of the three-dimensional structure can be controlled by varying the amount of radical initiator, thereby allowing the design of porous scaffolds tailored towards specific potential applications. This method also allows the fabrication of 3-D scaffolds using other carbon nanomaterials such as single-walled carbon nanotubes, fullerenes, and graphene indicating that it could be used as a versatile method for 3-D assembly of carbon nanostructures with pi bond networks.
Graphene has shown enormous potential for innovation in various research fields. The current chemical approaches based on exfoliation of graphite via graphite oxide (GO) are potential for large-scale synthesis of graphene but suffer from high cost, great operation difficulties, and serious waste discharge. We report a facile preparation of graphene by rapid reduction and expansion exfoliation of sulfuric acid intercalated graphite oxide (SIGO) at temperature just above 100°C in ambient atmosphere, noting that SIGO is easily available as the immediate oxidation descendent of graphite in sulfuric acid. The oxygenic and hydric groups in SIGO are mainly removed through dehydration as catalyzed by the intercalated sulfuric acid (ISA). The resultant consists of mostly single layer graphene sheets with a mean diameter of 1.07 μm after dispersion in DMF. This SIGO process is reductant free, easy operation, low-energy, environmental friendly and generates graphene with low oxygen content, less defect and high conductivity. The provided synthesis route from graphite to graphene via SIGO is compact and readily scalable.
The long spin diffusion length makes graphene very attractive for novel spintronic devices, and thus has triggered a quest for integrating the charge and spin degrees of freedom. However, ideal graphene is intrinsic non-magnetic, due to a delocalized π bonding network. Therefore, synthesis of ferromagnetic graphene or its derivatives with high magnetization is urgent due to both fundamental and technological importance. Here we report that N-doping can be an effective route to obtain a very high magnetization of ca. 1.66 emu/g, and can make graphene oxide (GO) to be ferromagnetism with a Curie-temperature of 100.2 K. Clearly, our findings can offer the easy realization of ferromagnetic GO with high magnetization, therefore, push the way for potential applications in spintronic devices.
In this article, we review gas sensor application of one-dimensional (1D) metal-oxide nanostructures with major emphases on the types of device structure and issues for realizing practical sensors. One of the most important steps in fabricating 1D-nanostructure devices is manipulation and making electrical contacts of the nanostructures. Gas sensors based on individual 1D nanostructure, which were usually fabricated using electron-beam lithography, have been a platform technology for fundamental research. Recently, gas sensors with practical applicability were proposed, which were fabricated with an array of 1D nanostructures using scalable micro-fabrication tools. In the second part of the paper, some critical issues are pointed out including long-term stability, gas selectivity, and room-temperature operation of 1D-nanostructure-based metal-oxide gas sensors.
1-dimensional nanostructures; gas sensors; long-term stability; gas selectivity; electronic-nose; room-temperature operation
Three-dimensional graphene architectures in the macroworld can in principle maintain all the extraordinary nanoscale properties of individual graphene flakes. However, current 3D graphene products suffer from poor electrical conductivity, low surface area and insufficient mechanical strength/elasticity; the interconnected self-supported reproducible 3D graphenes remain unavailable. Here we report a sugar-blowing approach based on a polymeric predecessor to synthesize a 3D graphene bubble network. The bubble network consists of mono- or few-layered graphitic membranes that are tightly glued, rigidly fixed and spatially scaffolded by micrometre-scale graphitic struts. Such a topological configuration provides intimate structural interconnectivities, freeway for electron/phonon transports, huge accessible surface area, as well as robust mechanical properties. The graphene network thus overcomes the drawbacks of presently available 3D graphene products and opens up a wide horizon for diverse practical usages, for example, high-power high-energy electrochemical capacitors, as highlighted in this work.
Three-dimensional graphene offers an ideal sheet-to-sheet connectivity of assembled graphenes, but often suffers from poor electrochemical performance. Wang et al. present a sugar-blowing technique to prepare a 3D graphene, which overcomes such problems and shows potential in supercapacitor applications.
Graphene is a single-atom thick, two-dimensional sheet of hexagonally arranged carbon atoms isolated from its three-dimensional parent material, graphite. One of the most common methods for preparation of graphene is chemical exfoliation of graphite using powerful oxidizing agents. Generally, graphene is synthesized through deoxygenation of graphene oxide (GO) by using hydrazine, which is one of the most widespread and strongest reducing agents. Due to the high toxicity of hydrazine, it is not a promising reducing agent in large-scale production of graphene; therefore, this study focused on a green or sustainable synthesis of graphene and the biocompatibility of graphene in primary mouse embryonic fibroblast cells (PMEFs).
Here, we demonstrated a simple, rapid, and green chemistry approach for the synthesis of reduced GO (rGO) from GO using triethylamine (TEA) as a reducing agent and stabilizing agent. The obtained TEA reduced GO (TEA-rGO) was characterized by ultraviolet (UV)–visible absorption spectroscopy, X-ray diffraction (XRD), particle size dynamic light scattering (DLS), scanning electron microscopy (SEM), Raman spectroscopy, and atomic force microscopy (AFM).
The transition of graphene oxide to graphene was confirmed by UV–visible spectroscopy. XRD and SEM were used to investigate the crystallinity of graphene and the surface morphologies of prepared graphene respectively. The formation of defects further supports the functionalization of graphene as indicated in the Raman spectrum of TEA-rGO. Surface morphology and the thickness of the GO and TEA-rGO were analyzed using AFM. The presented results suggest that TEA-rGO shows significantly more biocompatibility with PMEFs cells than GO.
This is the first report about using TEA as a reducing as well as a stabilizing agent for the preparation of biocompatible graphene. The proposed safe and green method offers substitute routes for large-scale production of graphene for several biomedical applications.
graphene oxide; graphene; triethylamine; ultraviolet; visible spectroscopy; Raman spectroscopy; atomic force microscopy
Neural stem cell (NSC) based therapy provides a promising approach for neural regeneration. For the success of NSC clinical application, a scaffold is required to provide three-dimensional (3D) cell growth microenvironments and appropriate synergistic cell guidance cues. Here, we report the first utilization of graphene foam, a 3D porous structure, as a novel scaffold for NSCs in vitro. It was found that three-dimensional graphene foams (3D-GFs) can not only support NSC growth, but also keep cell at an active proliferation state with upregulation of Ki67 expression than that of two-dimensional graphene films. Meanwhile, phenotypic analysis indicated that 3D-GFs can enhance the NSC differentiation towards astrocytes and especially neurons. Furthermore, a good electrical coupling of 3D-GFs with differentiated NSCs for efficient electrical stimulation was observed. Our findings implicate 3D-GFs could offer a powerful platform for NSC research, neural tissue engineering and neural prostheses.
Since graphene, a single sheet of graphite, has all of its carbon atoms on the surface, its property is very sensitive to materials contacting the surface. Herein, we report novel Raman peaks observed in annealed graphene and elucidate their chemical origins by Raman spectroscopy and atomic force microscopy (AFM). Graphene annealed in oxygen-free atmosphere revealed very broad additional Raman peaks overlapping the D, G and 2D peaks of graphene itself. Based on the topographic confirmation by AFM, the new Raman peaks were attributed to amorphous carbon formed on the surface of graphene by carbonization of environmental hydrocarbons. While the carbonaceous layers were formed for a wide range of annealing temperature and time, they could be effectively removed by prolonged annealing in vacuum. This study underlines that spectral features of graphene and presumably other 2-dimensional materials are highly vulnerable to interference by foreign materials of molecular thickness.
In this paper, we present a novel approach for the electrochemical detection of S-captopril based on graphene AuAg nanostructures used to modify an Au electrode. Multi-layer graphene (Gr) sheets decorated with embedded bimetallic AuAg nanoparticles were successfully synthesized catalytically with methane as the carbon source. The two catalytic systems contained 1.0 wt% Ag and 1.0 wt% Au, while the second had a larger concentration of metals (1.5 wt% Ag and 1.5 wt% Au) and was used for the synthesis of the Gr-AuAg-1 and Gr-AuAg-1.5 multicomponent samples. High-resolution transmission electron microscopy analysis indicated the presence of graphene flakes that had regular shapes (square or rectangular) and dimensions in the tens to hundreds of nanometers. We found that the size of the embedded AuAg nanoparticles varied between 5 and 100 nm, with the majority being smaller than 20 nm. Advanced scanning transmission electron microscopy studies indicated a bimetallic characteristic of the metallic clusters. The resulting Gr-AuAg-1 and Gr-AuAg-1.5 samples were used to modify the surface of commonly used Au substrates and subsequently employed for the direct electrochemical oxidation of S-captopril. By comparing the differential pulse voltammograms recorded with the two modified electrodes at various concentrations of captopril, the peak current was determined to be well-defined, even at relatively low concentration (10−5 M), for the Au/Gr-AuAg-1.5 electrode. In contrast, the signals recorded with the Au/Gr-AuAg-1 electrode were poorly defined within a 5×10−6 to 5×10−3 M concentration range, and many of them overlapped with the background. Such composite materials could find significant applications in nanotechnology, sensing, or nanomedicine.
bimetallic AuAg nanoparticles; electrochemical detection; multi-layer graphene
Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high–yield producing single– and multi–component large–scale three–dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter–sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large–scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large–scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials.
We report the application of palladium nanoparticles and thin films for hydrogen sensor. Electrochemically grown palladium particles with spherical shapes deposited on Si substrate and sputter deposited Pd thin films were used to detect hydrogen at room temperature. Grain size dependence of H2 sensing behavior has been discussed for both types of Pd films. The electrochemically grown Pd nanoparticles were observed to show better hydrogen sensing response than the sputtered palladium thin films. The demonstration of size dependent room temperature H2 sensing paves the ways to fabricate the room temperature metallic and metal–metal oxide semiconductor sensor by tuning the size of metal catalyst in mixed systems. H2 sensing by the Pd nanostructures is attributed to the chemical and electronic sensitization mechanisms.
Palladium; Hydrogen sensors
We report the application of palladium nanoparticles and thin films for hydrogen sensor. Electrochemically grown palladium particles with spherical shapes deposited on Si substrate and sputter deposited Pd thin films were used to detect hydrogen at room temperature. Grain size dependence of H2sensing behavior has been discussed for both types of Pd films. The electrochemically grown Pd nanoparticles were observed to show better hydrogen sensing response than the sputtered palladium thin films. The demonstration of size dependent room temperature H2sensing paves the ways to fabricate the room temperature metallic and metal–metal oxide semiconductor sensor by tuning the size of metal catalyst in mixed systems. H2sensing by the Pd nanostructures is attributed to the chemical and electronic sensitization mechanisms.
Palladium; Hydrogen sensors
Despite theoretical predictions, the question of room-temperature magnetic order in graphene must be conclusively resolved before graphene can fully achieve its potential as a spintronic medium. Through scanning tunneling microscopy (STM) and point I-V measurements, the current study reveals that unlike pristine samples, graphene nanostructures, when functionalized with aryl radicals, can sustain magnetic order. STM images show 1-D and 2-D periodic super-lattices originating from the functionalization of a single sub-lattice of the bipartite graphene structure. Field-dependent super-lattices in 3-nm wide “zigzag” nanoribbons indicate local moments with parallel and anti-parallel ordering along and across the edges, respectively. Anti-parallel ordering is observed in 2-D segments with sizes of over 20 nm. The field dependence of STM images and point I-V curves indicates a spin polarized local density of states (LDOS), an out-of-plane anisotropy field of less than 10 Oe, and an exchange coupling field of 100 Oe at room temperature.
Over the past decade, electrical detection of chemical and biological species using novel nanostructure-based devices has attracted significant attention for chemical, genomics, biomedical diagnostics, and drug discovery applications. The use of nanostructured devices in chemical/biological sensors in place of conventional sensing technologies has advantages of high sensitivity, low decreased energy consumption and potentially highly miniaturized integration. Owing to their particular structure, excellent electrical properties and high chemical stability, carbon nanotube and graphene based electrical devices have been widely developed for high performance label-free chemical/biological sensors. Here, we review the latest developments of carbon nanostructure-based transistor sensors in ultrasensitive detection of chemical/biological entities, such as poisonous gases, nucleic acids, proteins and cells.
chemical and biological sensors; carbon nanotubes; grapheme