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.
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.
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 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 has attracted much attention from researchers due to its interesting mechanical, electrochemical, and electronic properties. It has many potential applications such as polymer filler, sensor, energy conversion, and energy storage devices. Graphene-based nanocomposites are under an intense spotlight amongst researchers. A large amount of graphene is required for preparation of such samples. Lately, graphene-based materials have been the target for fundamental life science investigations. Despite graphene being a much sought-after raw material, the drawbacks in the preparation of graphene are that it is a challenge amongst researchers to produce this material in a scalable quantity and that there is a concern about its safety. Thus, a simple and efficient method for the preparation of graphene oxide (GO) is greatly desired to address these problems. In this work, one-pot chemical oxidation of graphite was carried out at room temperature for the preparation of large-area GO with ~100% conversion. This high-conversion preparation of large-area GO was achieved using a simplified Hummer’s method from large graphite flakes (an average flake size of 500 μm). It was found that a high degree of oxidation of graphite could be realized by stirring graphite in a mixture of acids and potassium permanganate, resulting in GO with large lateral dimension and area, which could reach up to 120 μm and ~8000 μm2, respectively. The simplified Hummer’s method provides a facile approach for the preparation of large-area GO.
graphene oxide; simplified Hummer’s method; chemical oxidation
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.
Crumpled graphene films are broadly used, for instance in electronics1, energy storage2, 3, composites4, 5, and biomedicine6. Although it is known that the degree of crumpling affects graphene's properties and the performance of graphene-based devices and materials3, 5, 7, the controlled folding and unfolding of crumpled graphene films has not been demonstrated. Here we report an approach to reversibly control the crumpling and unfolding of large-area graphene sheets. We show with experiments, atomistic simulations and theory that, by harnessing the mechanical instabilities of graphene adhered on a biaxially pre-stretched polymer substrate and by controlling the relaxation of the pre-strains in a particular order, graphene films can be crumpled into tailored self-organized hierarchical structures that mimic superhydrophobic leaves. The approach enables us to fabricate large-area conductive coatings and electrodes showing superhydrophobicity, high transparency, and tunable wettability and transmittance. We also demonstrate that crumpled graphene-polymer laminates can be used as artificial-muscle actuators.
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.
Thermoresponsive shape memory polymers (SMPs) are a type of stimuli-sensitive materials that switch from a temporary shape back to their permanent shape upon exposure to heat. While the majority of SMPs have been fabricated in the solid form, porous SMP foams exhibit distinct properties and are better suited for certain applications, including some in the biomedical field. Like solid SMPs, SMP foams have been restricted to a limited group of organic polymer systems. In this study, we prepared inorganic–organic SMP foams based on the photochemical cure of a macromer comprised of inorganic polydimethylsiloxane (PDMS) segments and organic poly(ε-caprolactone) (PCL) segments, diacrylated PCL40-block-PDMS37-block-PCL40. To achieve tunable pore size with high interconnectivity, the SMP foams were prepared via a refined solvent-casting/particulate-leaching (SCPL) method. By varying design parameters such as degree of salt fusion, macromer concentration in the solvent and salt particle size, the SMP foams with excellent shape memory behavior and tunable pore size, pore morphology, and modulus were obtained.
Polymeric materials; Porous materials; Shape memory materials
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
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.
Nanostructured surface possessing ultrahigh adhesion like “gecko foot” or “rose petal” can offer more opportunities for bionic application. We grow flower-like few-layer graphene on silicon nanocone arrays to form graphene nanoclusters, showing robust adhesion. Their contact angle (CA) is 164° with a hysteresis CA of 155° and adhesive force for a 5 μL water droplet is about 254 μN that is far larger than present reported results. We bring experimental evidences that this great adhesion depends on large-area plentiful edges of graphene nanosheets tuned by conical nanostructure and intrinsic wetting features of graphene. Such new hierarchical few-layer graphene nanostructure provides a feasible strategy to understand the ultra-adhesive mechanism of the “gecko effect” or “rose effect” and enhance the wettability of graphene for many practical applications.
This paper provides an overview of initial research conducted in the development of pressure-sensitive foam and its application in wearable sensing. The foam sensor is composed of polypyrrole-coated polyurethane foam, which exhibits a piezo-resistive reaction when exposed to electrical current. The use of this polymer-coated foam is attractive for wearable sensing due to the sensor's retention of desirable mechanical properties similar to those exhibited by textile structures.
The development of the foam sensor is described, as well as the development of a prototype sensing garment with sensors in several areas on the torso to measure breathing, shoulder movement, neck movement, and scapula pressure. Sensor properties were characterized, and data from pilot tests was examined visually.
The foam exhibits a positive linear conductance response to increased pressure. Torso tests show that it responds in a predictable and measurable manner to breathing, shoulder movement, neck movement, and scapula pressure.
The polypyrrole foam shows considerable promise as a sensor for medical, wearable, and ubiquitous computing applications. Further investigation of the foam's consistency of response, durability over time, and specificity of response is necessary.
Shape memory polymer (SMP) foam possesses structural and mechanical characteristics that make them very promising as an alternative treatment for intracranial aneurysms. Our SMP foams have low densities, with porosities as high as 98.8%; favorable for catheter delivery and aneurysm filling, but unfavorable for attenuating X-rays. This lack of contrast impedes the progression of this material becoming a viable medical device. This paper reports on increasing radioopacity by incorporating a high-Z element, tungsten particulate filler to attenuate X-rays, while conserving similar physical properties of the original non-opacified SMP foams. The minimal amount of tungsten for visibility was determined and subsequently incorporated into SMP foams, which were then fabricated into samples of increasing thicknesses. These samples were imaged through a pig’s skull to demonstrate radio-opacity in situ. Quantification of the increase in image contrast was performed via image processing methods and standard curves were made for varying concentrations of tungsten doped solid and foam SMP. 4% by volume loading of tungsten incorporated into our SMP foams has proven to be an effective method for improving radio-opacity of this material while maintaining the mechanical, physical and chemical properties of the original formulation.
Radio-opacity; Aneurysm; Coils; Shape memory polymer; Fluoroscopy
The functional layers of few-layer two-dimensional (2-D) thin flakes on flexible polymers for stretchable applications have attracted much interest. However, most fabrication methods are “indirect” processes that require transfer steps. Moreover, previously reported “transfer-free” methods are only suitable for graphene and not for other few-layer 2-D thin flakes. Here, a friction based room temperature rubbing method is proposed for fabricating different types of few-layer 2-D thin flakes (graphene, hexagonal boron nitride (h-BN), molybdenum disulphide (MoS2), and tungsten disulphide (WS2)) on flexible polymer substrates. Commercial 2-D raw materials (graphite, h-BN, MoS2, and WS2) that contain thousands of atom layers were used. After several minutes, different types of few-layer 2-D thin flakes were fabricated directly on the flexible polymer substrates by rubbing procedures at room temperature and without any transfer step. These few-layer 2-D thin flakes strongly adhere to the flexible polymer substrates. This strong adhesion is beneficial for future applications.
Chemical reduction of graphene oxide (GO) is the main route to produce the mass graphene-based materials with tailored surface chemistry and functions. However, the toxic reducing circumstances, multiple steps, and even incomplete removal of the oxygen-containing groups were involved, and the produced graphenes existed usually as the assembly-absent precipitates. Herein, a substrate-assisted reduction and assembly of GO (SARA-GO) method was developed for spontaneous formation of 3D graphene network on arbitrary conductive substrates including active and inert metals, semiconducting Si, nonmetallic carbon, and even indium-tin oxide glass without any additional reducing agents. The SARA-GO process offers a facile, efficient approach for constructing unique graphene assemblies such as microtubes, multi-channel networks, micropatterns, and allows the fabrication of high-performance binder-free rechargeable lithium-ion batteries. The versatile SARD-GO method significantly improves the processablity of graphenes, which could thus benefit many important applications in sensors and energy-related devices.
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
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
Photodetectors with ultrahigh sensitivity based on the composite made with all carbon-based materials consisting of graphite quantum dots (QDs), and two dimensional graphene crystal have been demonstrated. Under light illumination, remarkably, a photocurrent responsivity up to 4 × 107 AW−1 can be obtained. The underlying mechanism is attributed to the spatial separation of photogenerated electrons and holes due to the charge transfer caused by the appropriate band alignment across the interface between graphite QDs and graphene. Besides, the large absorptivity of graphite QDs and the excellent conductivity of the graphene sheet also play significant roles. Our result therefore demonstrates an outstanding illustration for the integration of the distinct properties of nanostructured carbon materials with different dimensionalities to achieve highly efficient devices. Together with the associated mechanism, it paves a valuable step for the further development of all carbon-based, cheap, and non-toxic optoelectronics devices with excellent performance.
Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges.