Showing papers by "Rodney S. Ruoff published in 2013"

Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

Abstract: Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...

The Role of Surface Oxygen in the Growth of Large Single-Crystal Graphene on Copper

Abstract: The growth of high-quality single crystals of graphene by chemical vapor deposition on copper (Cu) has not always achieved control over domain size and morphology, and the results vary from lab to lab under presumably similar growth conditions. We discovered that oxygen (O) on the Cu surface substantially decreased the graphene nucleation density by passivating Cu surface active sites. Control of surface O enabled repeatable growth of centimeter-scale single-crystal graphene domains. Oxygen also accelerated graphene domain growth and shifted the growth kinetics from edge-attachment–limited to diffusion-limited. Correspondingly, the compact graphene domain shapes became dendritic. The electrical quality of the graphene films was equivalent to that of mechanically exfoliated graphene, in spite of being grown in the presence of O.

Nanoporous Ni(OH)2 thin film on 3D Ultrathin-graphite foam for asymmetric supercapacitor.

Abstract: Nanoporous nickel hydroxide (Ni(OH)2) thin film was grown on the surface of ultrathin-graphite foam (UGF) via a hydrothermal reaction. The resulting free-standing Ni(OH)2/UGF composite was used as the electrode in a supercapacitor without the need for addition of either binder or metal-based current collector. The highly conductive 3D UGF network facilitates electron transport and the porous Ni(OH)2 thin film structure shortens ion diffusion paths and facilitates the rapid migration of electrolyte ions. An asymmetric supercapacitor was also made and studied with Ni(OH)2/UGF as the positive electrode and activated microwave exfoliated graphite oxide (‘a-MEGO’) as the negative electrode. The highest power density of the fully packaged asymmetric cell (44.0 kW/kg) was much higher (2–27 times higher), while the energy density was comparable to or higher, than high-end commercially available supercapacitors. This asymmetric supercapacitor had a capacitance retention of 63.2% after 10 000 cycles.

Activated Graphene-Based Carbons as Supercapacitor Electrodes with Macro- and Mesopores

Abstract: Electric double layer capacitors (or supercapacitors) store charges through the physisorption of electrolyte ions onto porous carbon electrodes. The control over structure and morphology of carbon electrode materials is therefore an effective strategy to render them high surface area and efficient paths for ion diffusion. Here we demonstrate the fabrication of highly porous graphene-derived carbons with hierarchical pore structures in which mesopores are integrated into macroporous scaffolds. The macropores were introduced by assembling graphene-based hollow spheres, and the mesopores were derived from the chemical activation with potassium hydroxide. The unique three-dimensional pore structures in the produced graphene-derived carbons give rise to a Brunauer–Emmett–Teller surface area value of up to 3290 m2 g–1 and provide an efficient pathway for electrolyte ions to diffuse into the interior surfaces of bulk electrode particles. These carbons exhibit both high gravimetric (174 F g–1) and volumetric (∼10...

Generation of B-doped graphene nanoplatelets using a solution process and their supercapacitor applications.

Abstract: Chemically modified graphene (CMG) nanoplatelets have shown great promise in various applications due to their electrical properties and high surface area. Chemical doping is one of the most effective methods to tune the electronic properties of graphene materials. In this work, novel B-doped nanoplatelets (borane-reduced graphene oxide, B-rG-O) were produced on a large scale via the reduction of graphene oxide by a borane-tetrahydrofuran adduct under reflux, and their use for supercapacitor electrodes was studied. This is the first report on the production of B-doped graphene nanoplatelets from a solution process and on the use of B-doped graphene materials in supercapacitors. The B-rG-O had a high specific surface area of 466 m2/g and showed excellent supercapacitor performance including a high specific capacitance of 200 F/g in aqueous electrolyte as well as superior surface area-normalized capacitance to typical carbon-based supercapacitor materials and good stability after 4500 cycles. Two- and three...

Enhancement of the Electrical Properties of Graphene Grown by Chemical Vapor Deposition via Controlling the Effects of Polymer Residue

Abstract: Residual polymer (here, poly(methyl methacrylate), PMMA) left on graphene from transfer from metals or device fabrication processes affects its electrical and thermal properties. We have found that the amount of polymer residue left after the transfer of chemical vapor deposited (CVD) graphene varies depending on the initial concentration of the polymer solution, and this residue influences the electrical performance of graphene field-effect transistors fabricated on SiO2/Si. A PMMA solution with lower concentration gave less residue after exposure to acetone, resulting in less p-type doping in graphene and higher charge carrier mobility. The electrical properties of the weakly p-doped graphene could be further enhanced by exposure to formamide with the Dirac point at nearly zero gate voltage and a more than 50% increase of the room-temperature charge carrier mobility in air. This can be attributed to electron donation to graphene by the −NH2 functional group in formamide that is absorbed in the polymer r...

Graphene-Encapsulated Si on Ultrathin-Graphite Foam as Anode for High Capacity Lithium-Ion Batteries

Abstract: A Si/graphene composite is drop-casted on an ultrathin-graphite foam (UGF) with three dimensional conductive network. The Si/graphene/UGF composite presents excellent stability and relatively high overall capacity when tested as an anode for rechargeable lithium ion batteries.

Millimeter-Size Single-Crystal Graphene by Suppressing Evaporative Loss of Cu During Low Pressure Chemical Vapor Deposition

Abstract: Millimeter-size single-crystal monolayer graphene is synthesized on polycrystalline Cu foil by a method that involves suppressing loss by evaporation of the Cu at high temperature under low pressure This significantly diminishes the number of graphene domains, and large single crystal domains up to ∼2 mm in size are grown

Metal contacts on physical vapor deposited monolayer MoS2

Abstract: The understanding of the metal and transition metal dichalcogenide (TMD) interface is critical for future electronic device technologies based on this new class of two-dimensional semiconductors. Here, we investigate the initial growth of nanometer-thick Pd, Au, and Ag films on monolayer MoS2. Distinct growth morphologies are identified by atomic force microscopy: Pd forms a uniform contact, Au clusters into nanostructures, and Ag forms randomly distributed islands on MoS2. The formation of these different interfaces is elucidated by large-scale spin-polarized density functional theory calculations. Using Raman spectroscopy, we find that the interface homogeneity shows characteristic Raman shifts in E2g1 and A1g modes. Interestingly, we show that insertion of graphene between metal and MoS2 can effectively decouple MoS2 from the perturbations imparted by metal contacts (e.g., strain), while maintaining an effective electronic coupling between metal contact and MoS2, suggesting that graphene can act as a c...

Reduced Graphene Oxide/Copper Nanowire Hybrid Films as High-Performance Transparent Electrodes

Abstract: Hybrid films composed of reduced graphene oxide (RG-O) and Cu nanowires (NWs) were prepared. Compared to Cu NW films, the RG-O/Cu NW hybrid films have improved electrical conductivity, oxidation resistance, substrate adhesion, and stability in harsh environments. The RG-O/Cu NW films were used as transparent electrodes in Prussian blue (PB)-based electrochromic devices where they performed significantly better than pure Cu NW films.

Inductive Tuning of Fano-Resonant Metasurfaces Using Plasmonic Response of Graphene in the Mid-Infrared

Abstract: Graphene is widely known for its anomalously strong broadband optical absorptivity of 2.3% that enables seeing its single-atom layer with the naked eye. However, in the mid-infrared part of the spectrum graphene represents a quintessential lossless zero-volume plasmonic material. We experimentally demonstrate that, when integrated with Fano-resonant plasmonic metasurfaces, single-layer graphene (SLG) can be used to tune their mid-infrared optical response. SLG’s plasmonic response is shown to induce large blue shifts of the metasurface’s resonance without reducing its spectral sharpness. This effect is explained by a generalized perturbation theory of SLG-metamaterial interaction that accounts for two unique properties of the SLG that set it apart from all other plasmonic materials: its anisotropic response and zero volume. These results pave the way to using gated SLG as a platform for dynamical spectral tuning of infrared metamaterials and metasurfaces.

A Platform for Large‐Scale Graphene Electronics – CVD Growth of Single‐Layer Graphene on CVD‐Grown Hexagonal Boron Nitride

Abstract: Direct chemical vapor deposition (CVD) growth of single-layer graphene on CVD-grown hexagonal boron nitride (h-BN) film can suggest a large-scale and high-quality graphene/h-BN film hybrid structure with a defect-free interface. This sequentially grown graphene/h-BN film shows better electronic properties than that of graphene/SiO2 or graphene transferred on h-BN film, and suggests a new promising template for graphene device fabrication.

Growth of Adlayer Graphene on Cu Studied by Carbon Isotope Labeling

Abstract: The growth of bilayer and multilayer graphene on copper foils was studied by isotopic labeling of the methane precursor. Isotope-labeled graphene films were characterized by micro-Raman mapping and time-of-flight secondary ion mass spectrometry. Our investigation shows that during growth at high temperature, the adlayers formed simultaneously and beneath the top, continuous layer of graphene and the Cu substrate. Additionally, the adlayers share the same nucleation center and all adlayers nucleating in one place have the same edge termination. These results suggest that adlayer growth proceeds by catalytic decomposition of methane (or CHx, x < 4) trapped in a “nano-chemical vapor deposition” chamber between the first layer and the substrate. On the basis of these results, submillimeter bilayer graphene was synthesized by applying a much lower growth rate.

Chlorination of Reduced Graphene Oxide Enhances the Dielectric Constant of Reduced Graphene Oxide/Polymer Composites

Abstract: 14–19 ] The conductor-insulator composites are attracting much attention for potential applications of charge-storage capacitors, thin-fi lm transistors, and antistatic materials owing to their unique properties, i.e., a dramatic increase in dielectric constant in the conductor-insulator composite fi lms near the percolation threshold.

25 GHz Embedded-Gate Graphene Transistors with High-K Dielectrics on Extremely Flexible Plastic Sheets

Abstract: Despite the widespread interest in graphene electronics over the past decade, high-performance graphene field-effect transistors (GFETs) on flexible substrates have been rarely achieved, even though this atomic sheet is widely understood to have greater prospects for flexible electronic systems. In this article, we report detailed studies on the electrical and mechanical properties of vapor synthesized high-quality monolayer graphene integrated onto flexible polyimide substrates. Flexible graphene transistors with high-k dielectric afforded intrinsic gain, maximum carrier mobilities of 3900 cm2/V·s, and importantly, 25 GHz cutoff frequency, which is more than a factor of 2.5 times higher than prior results. Mechanical studies reveal robust transistor performance under repeated bending, down to 0.7 mm bending radius, whose tensile strain is a factor of 2–5 times higher than in prior studies. In addition, integration of functional coatings such as highly hydrophobic fluoropolymers combined with the self-pas...

Integration of the Ferromagnetic Insulator EuO onto Graphene

Abstract: We have demonstrated the deposition of EuO films on graphene by reactive molecular beam epitaxy in a special adsorption-controlled and oxygen-limited regime, which is a critical advance toward the realization of the exchange proximity interaction (EPI). It has been predicted that when the ferromagnetic insulator (FMI) EuO is brought into contact with graphene, an overlap of electronic wavefunctions at the FMI/graphene interface can induce a large spin splitting inside the graphene. Experimental realization of this effect could lead to new routes for spin manipulation, which is a necessary requirement for a functional spin transistor. Furthermore, EPI could lead to novel spintronic behavior such as controllable magnetoresistance, gate tunable exchange bias, and quantized anomalous Hall effect. However, experimentally, EuO has not yet been integrated onto graphene. Here we report the successful growth of high quality crystalline EuO on highly-oriented pyrolytic graphite (HOPG) and single-layer graphene. The epitaxial EuO layers have (001) orientation and do not induce an observable D peak (defect) in the Raman spectra. Magneto-optic measurements indicate ferromagnetism with Curie temperature of 69 K, which is the value for bulk EuO. Transport measurements on exfoliated graphene before and after EuO deposition indicate only a slight decrease in mobility.

Near‐Field Enhanced Plasmonic‐Magnetic Bifunctional Nanotubes for Single Cell Bioanalysis

Abstract: Near-fi eld enhanced bifunctional plasmonic-magnetic (PM) nanostructures consisting of silica nanotubes with embedded solid nanomagnets and uniformly dual-surface-coated plasmonic Ag nanoparticles (NPs) are rationally synthesized. The solid embedded sections of nanotubes provide single-molecule sensitivity with an enhancement factor up to 7.2 × 10 9 for surfaceenhanced Raman scattering (SERS). More than 2 × SERS enhancement is observed from the hollow section compared to the solid section of the same nanotube. The substantial SERS enhancement on the hollow section is attributed to the dual-sided coating of Ag NPs as well as the near-fi eld optical coupling of Ag NPs across the nanotube walls. Experimentation and modeling are carried out to understand the dependence of SERS enhancement on the NP sizes, junctions, and the near fi eld effects. By tuning the aspect ratio of the embedded nanomagnets, the magnetic anisotropy of nanotubes can be readily controlled to be parallel or vertical to the long directions for nano-manipulation. Leveraging the bifunctionality, a nanotube is magnetically maneuvered to a single living mammalian cell amidst many and its membrane composition is analyzed via SERS spectroscopy.

High-volumetric performance aligned nano-porous microwave exfoliated graphite oxide-based electrochemical capacitors.

Abstract: Ultra-high volumetric performance electrochemical double layer capacitors based on high density aligned nano-porous microwave exfoliated graphite oxide have been studied. Elimination of macro-, meso-, and larger micro-pores from electrodes and controlling the nano-morphology results in very high volumetric capacitance, energy, and power density values.

Rapid Selective Etching of PMMA Residues from Transferred Graphene by Carbon Dioxide

Abstract: During chemical-vapor-deposited graphene transfer onto target substrates, a polymer film coating is necessary to provide a mechanical support. However, the remaining polymer residues after organic solvent rinsing cannot be effectively removed by the empirical thermal annealing in vacuum or forming gas. Little progress has been achieved in the past years, for little is known about the chemical evolution of the polymer macromolecules and their interaction with the environment. Through in situ Raman and infrared spectroscopy studies of PMMA transferred graphene annealed in nitrogen, two main processes are uncovered involving the polymer dehydrogenation below 200 °C and a subsequent depolymerization above 200 °C. Polymeric carbons over the monolayer graphitic carbon are found to constitute a fundamental bottleneck for a thorough etching of PMMA residues. The dehydrogenated polymeric chains consist of active C═C bonding sites that are readily attacked by oxidative gases. The combination of Raman spectroscopy, ...

Polysaccharide Nanocomposites Reinforced with Graphene Oxide and Keratin-Grafted Graphene Oxide

Abstract: Nanocomposites of polysaccharide matrices, chitosan–starch, and carboxymethyl cellulose-starch reinforced with graphene oxide and graphene grafted with keratin were developed. Composites films had been prepared for the casting/solvent evaporation method. The interaction and distribution of graphene materials in the biopolymer matrices were analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM), and the thermomechanical properties were examined using dynamic mechanical analysis. The nanocomposites of the chitosan–starch matrix improved their mechanical properties substantially, with respect to the film without reinforcing, obtaining an increase of 929% in the storage modulus (E′, 35 °C) with only 0.5 wt % of graphene oxide and outstanding increments in E′ at 150 and 200 °C when keratin-grafted graphene oxide is incorporated (0.1 wt %). In contrast, the graphene oxide incorporated into the carboxymethyl cellulose–starch matrix tends to decrease...

Graphene oxide nanoplatelet dispersions in concentrated NaCl and stabilization of oil/water emulsions.

Abstract: Stable dispersions of graphene oxide nanoplatelets were formed in water at pH 2–10 even with 5 wt% NaCl. For these conditions, oil-in-water emulsions stabilized with graphene oxide nanoplatelets remained partially stable for 1 year. The droplet sizes were as small as ∼1 μm with a low nanoplatelet concentration of 0.2 wt%. The emulsions were stable even for nanoplatelet concentrations down to 0.001 wt%. The stabilities of the emulsions even at high salinity may be attributed to the high anion density at the graphene oxide nanoplatelet edges which protrude into the water phase. Furthermore, the graphene oxide nanoplatelets are shown to adsorb on the surfaces of the oil droplets. The conceptual picture of graphene oxide nanoplatelets adsorbed to a greater extent on the water side of the oil/water interface, along with the high density of anions on their edges, cause the oil/water interface to curve about the oil phase, resulting in oil-in-water emulsion droplets. The dispersion stability with a very small amount of graphene oxide-based stabilizer, offers an intriguing opportunity for applications including CO2 sequestration and enhanced oil recovery in deep subsurface formations, which generally contain high-salinity brines.

Conversion of multilayer graphene into continuous ultrathin sp 3 -bonded carbon films on metal surfaces

Abstract: The conversion of multilayer graphenes into sp3-bonded carbon films on metal surfaces (through hydrogenation or fluorination of the outer surface of the top graphene layer) is indicated through first-principles computations. The main driving force for this conversion is the hybridization between sp3 orbitals and metal surface dz2 orbitals. The induced electronic gap states and spin moments in the carbon layers are confined in a region within 0.5 nm of the metal surface. Whether the conversion occurs depend on the fraction of hydrogenated (fluorinated) C atoms at the outer surface and on the number of stacked graphene layers. In the analysis of the Eliashberg spectral functions for the sp3 carbon films on a metal surface that is diamagnetic, the strong covalent metal-sp3 carbon bonds induce soft phonon modes that predominantly contribute to large electron-phonon couplings, suggesting the possibility of phonon-mediated superconductivity. Our computational results suggest a route to experimental realization of large-area ultrathin sp3-bonded carbon films on metal surfaces.

Van der Waals Epitaxial Double Heterostructure: InAs/Single‐Layer Graphene/InAs

Abstract: Van der Waals (vdW) epitaxial double heterostructures have been fabricated by vdW epitaxy of InAs nanostructures on both sides of graphene. InAs nanostructures diametrically form on/underneath graphene exclusively along As-polar direction, indicating polarity inversion of the double heterostructures. First-principles and density functional calculations demonstrate how and why InAs easily form to be double heterostructures with polarity inversion.

Graphene synthesis via magnetic inductive heating of copper substrates.

Abstract: Scaling graphene growth using an oven to heat large substrates becomes less energy efficient as system size is increased. We report a route to graphene synthesis in which radio frequency (RF) magnetic fields inductively heat metal foils, yielding graphene of quality comparable to or higher than that of current chemical vapor deposition techniques. RF induction heating allows for rapid temperature ramp up/down, with great potential for large scale and rapid manufacturing of graphene with much better energy efficiency. Back-gated field effect transistors on a SiO2/Si substrate showed carrier mobility up to ∼14 000 cm2 V–1 s–1 measured under ambient conditions. Many advantages of RF heating are outlined, and some fundamental aspects of this approach are discussed.