Jinho An

Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils

Growing Graphene The highest quality graphene samples, single-atom-thick layers of carbon, are suspended flakes exfoliated from graphite, but these samples are very small in size (square micrometers). For many electronics applications, larger areas are needed. Li et al. (p. 1312, published online 7 May) show that graphene grows in a self-limiting way on copper films as large-area sheets (one square centimeter) from methane through a chemical vapor deposition process. The films, which are mainly one layer in thickness, can be transferred to other substrates and have electron mobilities as high as 4300 square centimeters per volt second. Predominantly single-layer graphene films grow in a self-limited manner on copper and can be transferred to other substrates. Graphene has been attracting great interest because of its distinctive band structure and physical properties. Today, graphene is limited to small sizes because it is produced mostly by exfoliating graphite. We grew large-area graphene films of the order of centimeters on copper substrates by chemical vapor deposition using methane. The films are predominantly single-layer graphene, with a small percentage (less than 5%) of the area having few layers, and are continuous across copper surface steps and grain boundaries. The low solubility of carbon in copper appears to help make this growth process self-limiting. We also developed graphene film transfer processes to arbitrary substrates, and dual-gated field-effect transistors fabricated on silicon/silicon dioxide substrates showed electron mobilities as high as 4050 square centimeters per volt per second at room temperature.

Graphene-Based Ultracapacitors

The surface area of a single graphene sheet is 2630 m(2)/g, substantially higher than values derived from BET surface area measurements of activated carbons used in current electrochemical double layer capacitors. Our group has pioneered a new carbon material that we call chemically modified graphene (CMG). CMG materials are made from 1-atom thick sheets of carbon, functionalized as needed, and here we demonstrate in an ultracapacitor cell their performance. Specific capacitances of 135 and 99 F/g in aqueous and organic electrolytes, respectively, have been measured. In addition, high electrical conductivity gives these materials consistently good performance over a wide range of voltage scan rates. These encouraging results illustrate the exciting potential for high performance, electrical energy storage devices based on this new class of carbon material.

Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide

The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13–labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

Graphene Films with Large Domain Size by a Two-Step Chemical Vapor Deposition Process

The fundamental properties of graphene are making it an attractive material for a wide variety of applications. Various techniques have been developed to produce graphene and recently we discovered the synthesis of large area graphene by chemical vapor deposition (CVD) of methane on Cu foils. We also showed that graphene growth on Cu is a surface-mediated process and the films were polycrystalline with domains having an area of tens of square micrometers. In this paper, we report on the effect of growth parameters such as temperature, and methane flow rate and partial pressure on the growth rate, domain size, and surface coverage of graphene as determined by Raman spectroscopy, and transmission and scanning electron microscopy. On the basis of the results, we developed a two-step CVD process to synthesize graphene films with domains having an area of hundreds of square micrometers. Scanning electron microscopy and Raman spectroscopy clearly show an increase in domain size by changing the growth parameters. Transmission electron microscopy further shows that the domains are crystallographically rotated with respect to each other with a range of angles from about 13 to nearly 30°. Electrical transport measurements performed on back-gated FETs show that overall films with larger domains tend to have higher carrier mobility up to about 16,000 cm(2) V(-1) s(-1) at room temperature.

Biocompatible, robust free-standing paper composed of a TWEEN/graphene composite.

Nonspecific binding (NSB), a random adsorption of biocomponents such as proteins and bacteria on noncomplementary materials,isoneofthebiggestproblemsinbiological applications including biosensors, protein chips, surgical instruments, drug delivery, and biomedicine. Polyoxyethylene sorbitan laurate (TWEEN), a commercially available chemical with aliphatic ester chains, has shown promise as a medical material and in overcomingproblems associated withNSB. [1‐4] However,stability during solution-based processing and uniformity of the materials that have TWEEN coating on flat substrates or nanomaterials using the selfassembled-monolayer (SAM) method has been an important issue. Further, biocompatible materials with high strength are important for several medical applications including stents, nail implants, and strong invasive instruments. Here, we present the production of a free-standing ‘‘paperlike’’ material composed of TWEEN and reduced graphene oxide (RGO) platelets and obtained by simple filtration of a homogeneous aqueous colloidal suspension of TWEEN/RGO hybrid. The ‘‘TWEEN paper’’ was highly stable in water without leakage of TWEEN and is compliant and sufficiently robust to be handled by hand without breaking. Furthermore, the TWEEN paper was noncytotoxic to three mammalian cell lines and biocompatible, inhibiting nonspecific binding of Gram-positive bacteria. [5] In contrast, RGO paper without TWEEN showed nonspecific bacterial binding. TWEEN is composed ofthree chemical parts (Fig. 1a): aliphatic esterchains that can prevent NSB ofbiomolecules, three-terminal hydroxyl groups that are hydrophilic and can be chemically modified for further applications, and an aliphatic chain that can easily be adsorbed on a hydrophobic surface by noncovalent interaction. Protein microarrays on flat substrates with SAM of TWEEN [4] and highly sensitive biosensors, [1‐3] built using field-effect transistor (FET) behavior of individual carbon nanotube (CNT) strands coated with TWEEN, have demonstrated that TWEEN can be effectively used to overcome NSB.

Polymer Brushes via Controlled, Surface‐Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide

A method for growing polymers directly from the surface of graphene oxide is demonstrated. The technique involves the covalent attachment of an initiator followed by the polymerization of styrene, methyl methacrylate, or butyl acrylate using atom transfer radical polymerization (ATRP). The resulting materials were characterized using a range of techniques and were found to significantly improve the solubility properties of graphene oxide. The surface-grown polymers were saponified from the surface and also characterized. Based on these results, the ATRP reactions were determined to proceed in a controlled manner and were found to leave the structure of the graphene oxide largely intact.

Raman Measurements of Thermal Transport in Suspended Monolayer Graphene of Variable Sizes in Vacuum and Gaseous Environments

Using micro-Raman spectroscopy, the thermal conductivity of a graphene monolayer grown by chemical vapor deposition and suspended over holes with different diameters ranging from 2.9 to 9.7 μm was measured in vacuum, thereby eliminating errors caused by heat loss to the surrounding gas. The obtained thermal conductivity values of the suspended graphene range from (2.6 ± 0.9) to (3.1 ± 1.0) × 10(3) Wm(-1)K(-1) near 350 K without showing the sample size dependence predicted for suspended, clean, and flat graphene crystal. The lack of sample size dependence is attributed to the relatively large measurement uncertainty as well as grain boundaries, wrinkles, defects, or polymeric residue that are possibly present in the measured samples. Moreover, from Raman measurements performed in air and CO(2) gas environments near atmospheric pressure, the heat transfer coefficient for air and CO(2) was determined and found to be (2.9 +5.1/-2.9) and (1.5 +4.2/-1.5) × 10(4) Wm(-2)K(-1), respectively, when the graphene temperature was heated by the Raman laser to about 510 K.

Graphene‐Based Actuators

The development of new mechanical actuators that convert external stimuli such as thermal, light, electrical, or chemical energy to mechanical energy depends on the development of new materials. Reversible mechanical actuators based on carbon nanotubes (CNTs) and hydrogel polymers have suggested applications in robotics, sensors, mechanical instruments, microscopy tips, switches, and memory chips. Recently, electromechanical resonators composed of singleand multilayer graphene sheets were reported. We present here a novel macroscopic graphene-based actuator that shows actuation that depends on variation of humidity and/or temperature. The actuator is a free standing ‘‘paper-like’’ material made by sequential filtration of CNT, and then graphene oxide, aqueous colloidal suspensions. ‘‘Paper-like’’ materials composed of stacked graphene oxide platelets produced by simple filtration of an aqueous graphene oxide suspension exhibited good mechanical properties, with a modulus of about 40 GPa and a fracture strength of about 130 MPa. Chemical modification of graphene oxide paper with divalent ions can enhance its mechanical properties. Based on these results that show excellent mechanical properties of individual graphene sheets and of paper-like materials composed of them, we have tried to make mechanical actuators by using graphene oxide platelets. Graphite oxide (GO) is generated by oxidation of graphite and contains a wide range of oxygen functional groups, such as hydroxyl and epoxy groups on the basal plane and carboxylic acid groups at the edges, which make the GO hydrophilic. The oxygen functional groups in the GO, which contains a layered structure of graphene oxide platelets, allow dynamic intercalation of water molecules into the gallery between the layers. The interlayer distance between the graphite oxides reversibly varies from 6 to 12 A depending on the relative humidity, with increased interlayer distance as the relative humidity increases. Graphene oxide paper contains a layered structure similar to, but not identical to, GO (the coherence length in the paperlike material is 6–7 platelets,

Site-specific deposition of Au nanoparticles in CNT films by chemical bonding.

There has been no attempt to date to specifically modify the nodes in carbon nanotube (CNT) networks. If the nodes can be modified in favorable ways, the electrical and/or thermal and/or mechanical properties of the CNT networks could be improved. In an attempt to influence the performance as a transparent conductive film, gold nanoparticles capped with the amino acid cysteine (Au-CysNP) have been selectively attached at the nodes of multiwalled carbon nanotubes (MWCNTs) networks. These nanoparticles have an average diameter of 5 nm as observed by TEM. FTIR and XPS were used to characterize each step of the MWCNT chemical functionalization process. The chemical process was designed to favor selective attachment at the nodes and not the segments in the CNT networks. The chemical processing was designed to direct formation of nodes where the gold nanoparticles are. The nanoparticles which were loosely held in the CNT network could be easily washed away by solvents, while those bound chemically remained. TEM results show that the Cys-AuNPs are preferentially located at the nodes of the CNT networks when compared to the segments. These nanoparticles at the nodes were also characterized by a novel technique called diffraction scanning transmission electron microscopy (D-STEM) confirming their identity. Four-probe measurements found that the sheet resistance of the modified CNT networks was half that of similarly transparent pristine multiwalled CNT networks.

Finite element modeling of stress variation in multilayer thin-film specimens for in situ transmission electron microscopy experiments

Multilayer thin-film materials with various thicknesses, compositions, and deposition methods for each layer typically exhibit residual stresses. In situ transmission electron microscopy (TEM) is a powerful technique that has been used to determine correlations between residual stresses and the microstructure. However, to produce electron transparent specimens for TEM, one or more layers of the film are sacrificed, thus altering the state of stresses. By conducting a stress analysis of multilayer thin-film TEM specimens, using a finite element method, we show that the film stresses can be considerably altered after TEM sample preparation. The stress state depends on the geometry and the interactions among multiple layers.