Ultimate strength, ripples, sound velocities, and density of phonon states of strained graphene

We study the dispersion characteristics of strained graphene using many-body interatomic potentials and find: (i) borders of the structural stability of a flat graphene in the three-dimensional space of the strain components (ε_xx, ε_yy, ε_xy); (ii) sound velocities of strained graphene; and (iii) phonon density of states (DOS) of strained graphene. The border of structural stability of flat graphene is also presented in the space of components of normal and shear membrane forces (T_x, T_y, T_xy). We find that flat graphene is structurally stable under elastic strain up to 0.3-0.4, but it becomes unstable to a shear strain in the absence of tensile components of strain. Also graphene cannot remain flat under compressive membrane forces because its bending stiffness vanishes. We employ the molecular dynamics simulations to study the post-critical behavior of graphene. We demonstrate that ripples with controllable amplitude and orientation can be generated under simultaneous action of shear and tensile membrane forces. Gaps in the phonon DOS are observed when graphene is strained close to the appearance of ripples. Sound velocities of unstrained graphene do not depend on the propagation direction but application of strain makes graphene anisotropic. One of the sound velocities vanishes at the border of the structural stability of graphene meaning that vanishing of sound velocity (or corresponding elastic constant) predicts impending instability.     

石墨烯的制备方法及其应用特性

近3年来,石墨烯以其独特的结构和优异的性能,在化学、物理和材料学界引起了轰动。引用大量最新的参考文献,介绍了石墨烯的研究现状,通过评述石墨烯的合成、功能化以及近期应用概况,展望了石墨烯的发展前景和研究方向,认为借鉴各种方法的优势,综合运用,可以制备单层、结构完整和高电导率的石墨烯,并进一步将其功能化,拓展其应用领域并已取得较大的进展,这一途径被认为是石墨烯规模化应用的战略起点。     

Vertically-aligned graphene flakes on nanoporous templates: morphology,thickness, and defect level control by pre-treatment

Various morphologies of the vertically-aligned graphene flakes were fabricated on the nanoporous templates treated with metal ions in solutions, as well as coated with a thin gold layer and activated in the low-temperature Ar plasma. The thickness and level of structural defects in the graphene flakes could be effectively controlled by a proper selection of the pre-treatment method. We have also demonstrated that various combinations of the flake thickness and defect levels can be obtained, and the morphology and density of the graphene pattern can be effectively controlled. The result obtained could be of interest for various applications requiring fabrication of large graphene networks with controllable properties.     

Preparation, characterization, and electrocatalytic performance of graphene-methylene blue thin films

We report a general method to graft aromatic molecules onto graphene thin film electrodes through a simple immersion process. Large-area electroactive graphene thin films grafted with methylene blue (MB) have been developed as electrocatalytic electrodes for the oxidation of β-nicotinamide adenine dinucleotide (NADH). The oxidation of NADH starts from −0.08 V (vs. Ag/AgCl) at the graphene-MB thin film electrodes, showing a decrease of 530 mV in overpotential compared to a Ti metal electrode. The graphene-MB thin films have promising applications in biosensors and biofuel cells due to their ability to promote NADH electron transfer reaction.     

Vapor trapping growth of single-crystalline graphene flowers: synthesis, morphology, and electronic properties

We report a vapor trapping method for the growth of large-grain, single-crystalline graphene flowers with grain size up to 100 μm. Controlled growth of graphene flowers with four lobes and six lobes has been achieved by varying the growth pressure and the methane to hydrogen ratio. Surprisingly, electron backscatter diffraction study revealed that the graphene morphology had little correlation with the crystalline orientation of underlying copper substrate. Field effect transistors were fabricated based on graphene flowers and the fitted device mobility could achieve ～4200 cm(2) V(-1) s(-1) on Si/SiO(2) and ～20?000 cm(2) V(-1 )s(-1) on hexagonal boron nitride (h-BN). Our vapor trapping method provides a viable way for large-grain single-crystalline graphene synthesis for potential high-performance graphene-based electronics.     

Synthesis of large-area, few-layer graphene on iron foil by chemical vapor deposition

We demonstrate a simple and controllable way to synthesize large-area, few-layer graphene on iron substrates by an optimized chemical vapor deposition (CVD) method using a mixture of methane and hydrogen. Based on an analysis of the Fe-C phase diagram, a suitable procedure for the successful synthesis of graphene on Fe surfaces was designed. An appropriate temperature and cooling process were found to be very important in the synthesis of highly crystalline few-layer graphene. Graphene-based field-effect transistor (FET) devices were fabricated using the resulting few-layer graphene, and showed good quality with extracted mobilities of 300–1150 cm²/(V·s).      

Conductive,self-cleaning,and short-circuit proof multi-functional graphene aerogel composite fibers

This work reports the superior properties of flexible multi-functional composite fibers based on graphene aerogel fibers. With the addition of phase change materials, the graphene aerogel fibers were synthesized by wet spinning and supercritical drying. The phase change materials can improve the structural uniformity and thermal stability of the composite fibers. The fibers coated with polydimethylsiloxane and fluorocarbon can respond to various external stimuli (e.g., electrons, photons, and heat), as well as have excellent properties of shape compliance, self-cleaning, and insulated surfaces. After coating fluorocarbon, the maximum water contact angle of graphene aerogel fibers increases from 132.18° to 151.77°. It is worth mentioning that adding an insulation layer of polydimethylsiloxane avoids the high-temperature problem caused by the short circuit of graphene aerogel fibers. The short-circuit temperature of graphene aerogel fibers is as high as 65 °C, while that of the composite fiber is only 41.5 °C after coating with polydimethylsiloxane. The temperature of graphene aerogel fibers with polyethylene glycol can increase to 39.3 °C under simulated sunlight. In addition, graphene aerogel fibers have excellent electrical conductivity (4.85?×?10³ S m^?1) at 300 K. After coating with polyethylene glycol, its electrical conductivity is still as high as 2.95?×?10³ S m^?1. The good electrical conductivity makes the aerogel fibers have promising application in advanced wearable systems.

     

Interplay of wrinkles, strain, and lattice parameter in graphene on iridium

Following graphene growth by thermal decomposition of ethylene on Ir(111) at high temperatures we analyzed the strain state and the wrinkle formation kinetics as function of temperature. Using the moiré spot separation in a low energy electron diffraction pattern as a magnifying mechanism for the difference in the lattice parameters between Ir and graphene, we achieved an unrivaled relative precision of ±0.1 pm for the graphene lattice parameter. Our data reveals a characteristic hysteresis of the graphene lattice parameter that is explained by the interplay of reversible wrinkle formation and film strain. We show that graphene on Ir(111) always exhibits residual compressive strain at room temperature. Our results provide important guidelines for strategies to avoid wrinkling.     

Complex structure of triangular graphene: electronic, magnetic and electromechanical properties

We have investigated electronic and magnetic properties of graphene nanodisks (nanosize triangular graphene) as well as electromechanical properties of graphene nanojunctions. Nanodisks are nanomagnets made of graphene, which are robust against perturbation such as impurities and lattice defects, where the ferromagnetic order is assured by Lieb's theorem. We can generate a spin current by spin filter, and manipulate it by a spin valve, a spin switch and other spintronic devices made of graphene nanodisks. We have analyzed nanodisk arrays, which have multi-degenerate perfect flat bands and are ferromagnet. By connecting two triangular graphene corners, we propose a nanomechanical switch and rotator, which can detect a tiny angle rotation by measuring currents between the two corners. By making use of the strain induced Peierls transition of zigzag nanoribbons, we also propose a nanomechanical stretch sensor, in which the conductance can be switched off by a nanometer scale stretching.     

Recent Advances of Porous Graphene: Synthesis,Functionalization, and Electrochemical Applications

Graphene is a 2D sheet of sp² bonded carbon atoms and tends to aggregate together, due to the strong π–π stacking and van der Waals attraction between different layers. Its unique properties such as a high specific surface area and a fast mass transport rate are severely blocked. To address these issues, various kinds of 2D holey graphene and 3D porous graphene are either self‐assembled from graphene layers or fabricated using graphene related materials such as graphene oxide and reduced graphene oxide. Porous graphene not only possesses unique pore structures, but also introduces abundant exposed edges and accelerates mass transfer. The properties and applications of these porous graphenes and their composites/hybrids have been extensively studied in recent years. Herein, recent progress and achievements in synthesis and functionalization of various 2D holey graphene and 3D porous graphene are reviewed. Of special interest, electrochemical applications of porous graphene and its hybrids in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage, are highlighted. As the closing remarks, the challenges and opportunities for the future research of porous graphene and its composites are discussed and outlined.     

Coupling of short DNAs with reduced graphene oxide for electronic and sensing applications

Abstract

In this article, we described an approach for coupling of short DNAs with reduced graphene oxide and thus formation of transducer layer for biological sensors. We investigated the dependence of coupling ratio on the graphene oxide reduction level. We found optimal reduction parameters and showed successful conjugation of aptamers with reduced graphene oxide. We have revealed a trend to increase aptamer conjugation efficiency with a decrease of graphene oxide reduction rate. Finally, we made biosensor structures with Π-shaped reduction pattern and showed excellent sensitivity of the sensor during thrombin exposure. These results are important for the development of flexible low-cost biosensors of a new generation.     

R6G on graphene: high Raman detection sensitivity, yet decreased Raman cross-section

Several recent studies have demonstrated the use of single and few-layer graphene as a substrate for the enhancement of Raman scattering by adsorbed molecules in a method termed graphene-enhanced Raman spectroscopy (GERS). Here we determine the resonance Raman scattering cross-section for the dye molecule rhodamine 6G (R6G) adsorbed on bilayer graphene. For the 1650 cm(-1) R6G mode, we obtain a cross-section of 5.1 × 10(-24) cm(2)·molecule(-1), a greater than 3-fold reduction from the previously reported solution value. We show that the absorption spectrum of adsorbed R6G can be measured using micro-optical contrast spectroscopy, and we find that detuning of the molecular resonance explains the decreased Raman scattering cross-section. We find no evidence for a graphene Raman enhancement process. We also study the graphene thickness dependence of the adsorbed R6G Raman signal and show that a model incorporating electromagnetic interference effects can qualitatively explain the decrease in signal with increasing graphene thickness.     

Graphene Microbolometers with Superconducting Contacts for Terahertz Photon Detection

We report on noise and thermal conductance measurements taken in order to determine an upper bound on the performance of graphene as a terahertz photon detector. The main mechanism for sensitive terahertz detection in graphene is bolometric heating of the electron system. To study the properties of a device using this mechanism to detect terahertz photons, we perform Johnson noise thermometry measurements on graphene samples. These measurements probe the electron–phonon behavior of graphene on silicon dioxide at low temperatures. Because the electron–phonon coupling is weak in graphene, superconducting contacts with large gap are used to confine the hot electrons and prevent their out-diffusion. We use niobium nitride leads with a \(T_\mathrm {c}\approx 10\)  K to contact the graphene. We find these leads make good ohmic contact with very low contact resistance. Our measurements find an electron–phonon thermal conductance that depends quadratically on temperature above 4 K and is compatible with single terahertz photon detection.     

Simulation of ripples in single layer graphene sheets and study of their vibrational and elastic properties

We present the results of our theoretical investigation on ripples and elastic properties of single layer graphene sheets in both membrane and ribbon conformations. The formation of ripples in both the systems is simulated and analyzed using two-dimensional vibrating membrane model. We have chosen both square graphene membrane, armchair and zigzag graphene nanoribbons with different sizes. The amplitude of vibrational modes of each system is determined using this model. We observed that the vertical displacement (amplitude of the ripples) reaches a maximum height of about 0.99 nm from the mean plane in both conformations whose lengths are integral multiple of the basic armchair/zigzag units. We have studied the dynamical elastic properties through the calculation of parameters like normalized stiffness, speed parameter, Cauchy number and critical velocity with reference to a new aspect ratio of graphene sheets. We have made correlations between the calculated parameters with the formation of ripples and found that the out-of-plane deformations are spontaneous and significant in square conformation of graphene than the graphene nanoribbons. The vibrational modes obtained for GNRs and membranes are acoustic modes. The results of our study will be very much useful in selecting graphene sheets with suitable conformation and chirality for designing nanoscale devices.     

Mapping the nanomechanical properties of graphene suspended on silica nanoparticles

Using nanoparticles to impart extrinsic rippling in graphene is a relatively new method to induce strain and to tailor the properties of graphene. Here, we study the structure and elastic properties of graphene grown by chemical vapour deposition and transferred onto a continuous layer of SiO₂ nanoparticles with diameters of around 25 nm, prepared by Langmuir–Blodgett technique on Si substrate. We show that the transferred graphene follows only roughly the morphology induced by nanoparticles. The graphene membrane parts bridging the nanoparticles are suspended and their adhesion to the atomic force microscope tip is larger compared to that of supported graphene parts. These suspended graphene regions can be deformed with forces of the order of 10 nN. The elastic modulus of graphene was determined from indentation measurements performed on suspended membrane regions with diameters in the 100 nm range.     

Surface charge induced tuning of electrical properties of CVD assisted graphene and functionalized graphene sheets

We demonstrate a new approach to tune the electrical properties of graphene and functionalized graphene. Graphene was synthesized using thermal chemical vapour deposition(TCVD) method on copper foil using precursor gas acetylene and co-catalyst H2 gas. TCVD assisted graphene was successfully transferred onto a silicon wafer. Transferred graphene sheet was then functionalized to prepare graphene oxide(GO) and reduced graphene oxide(rGO). Different surface charge carbon nanoparticles, e.g. carbon nanoparticle with net positive charge and carbon nanoparticle with net negative charge were then immobilized on transferred graphene and functionalized graphene sheets. The functionalized graphene and charge mobilized functionalized graphene were characterized by Uv–vis spectroscopy,Fourier transformed infrared spectroscopy, scanning electron microscopy, and Raman spectroscopy. After immobilization of carbon nanomaterials, the ac electrical conductivity was found to increase due to enhancement of the surface charge, electron density, and mobility. It was observed that negative surface charge immobilized graphene and functionalized graphene show higher conductivity. Thus, the electrical property of graphene and functionalized graphene can be tuned by surface modification with different surface charge carbon nanomaterials.     

Is graphene aromatic?

We analyze the chemical bonding in graphene using a fragmental approach, the adaptive natural density partitioning method, electron sharing indices, and nucleus-independent chemical shift indices. We prove that graphene is aromatic, but its aromaticity is different from the aromaticity in benzene, coronene, or circumcoronene. Aromaticity in graphene is local with two π-electrons delocalized over every hexagon ring. We believe that the chemical bonding picture developed for graphene will be helpful for understanding chemical bonding in defects such as point defects, single-, double-, and multiple vacancies, carbon adatoms, foreign adatoms, substitutional impurities, and new materials that are derivatives of graphene.      

Synthesis, Transfer, and Devices of Single- and Few-Layer Graphene by Chemical Vapor Deposition

The advance of graphene-based nanoelectronics has been hampered due to the difficulty in producing single- or few-layer graphene over large areas. We report a simple, scalable, and cost-efficient method to prepare graphene using methane-based CVD on nickel films deposited over complete $hbox{Si/SiO}_{2}$ wafers. By using highly diluted methane, single- and few-layer graphene were obtained, as confirmed by micro-Raman spectroscopy. In addition, a transfer technique has been applied to transfer the graphene film to target substrates via nickel etching. FETs based on the graphene films transferred to $hbox{Si/SiO}_{2}$ substrates revealed a weak p-type gate dependence, while transferring of the graphene films to glass substrate allowed its characterization as transparent conductive films, exhibiting transmittance of 80% in the visible wavelength range.      

Effects of methane flux on structural and transport properties of CVD-grown graphene films

Large area, single-layer graphene films were synthesized on copper foils by chemical vapor deposition. We have investigated the effects of methane flux on structural and transport properties of graphene. Raman spectra and electrical results reveal that methane flux has almost no influence on the thickness of graphene, but clearly influences the structural defects of graphene. In addition, graphene field effect transistors with a gate length of 10 μm were fabricated, exhibiting obvious field effects and p-type characteristics.     

Vapour-phase graphene epitaxy at low temperatures

We report an epitaxial growth of graphene, including homo- and hetero-epitaxy on graphite and SiC substrates, at a temperature as low as ∼540 °C. This vapour-phase epitaxial growth, carried out in a remote plasma-enhanced chemical vapor deposition (RPECVD) system using methane as the carbon source, can yield large-area high-quality graphene with the desired number of layers over the entire substrate surfaces following an AB-stacking layer-by-layer growth model. We also developed a facile transfer method to transfer a typical continuous one layer epitaxial graphene with second layer graphene islands on top of the first layer with the coverage of the second layer graphene islands being 20% (1.2 layer epitaxial graphene) from a SiC substrate onto SiO₂ and measured the resistivity, carrier density and mobility. Our work provides a new strategy toward the growth of graphene and broadens its prospects of application in future electronics.