Ji Won Suk

Graphene and Graphene Oxide: Synthesis, Properties, and Applications

There is intense interest in graphene in fields such as physics, chemistry, and materials science, among others. Interest in graphenes exceptional physical properties, chemical tunability, and potential for applications has generated thousands of publications and an accelerating pace of research, making review of such research timely. Here is an overview of the synthesis, properties, and applications of graphene and related materials (primarily, graphite oxide and its colloidal suspensions and materials made from them), from a materials science perspective.

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.

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.

Improved Electrical Conductivity of Graphene Films Integrated with Metal Nanowires

Polycrystalline graphene grown by chemical vapor deposition (CVD) on metals and transferred onto arbitrary substrates has line defects and disruptions such as wrinkles, ripples, and folding that adversely affect graphene transport properties through the scattering of the charge carriers. It is found that graphene assembled with metal nanowires (NWs) dramatically decreases the resistance of graphene films. Graphene/NW films with a sheet resistance comparable to that of the intrinsic resistance of graphene have been obtained and tested as a transparent electrode replacing indium tin oxide films in electrochromic (EC) devices. The successful integration of such graphene/NW films into EC devices demonstrates their potential for a wide range of optoelectronic device applications.

Synthesis and characterization of large-area graphene and graphite films on commercial Cu-Ni alloy foils.

Controlling the thickness and uniformity during growth of multilayer graphene is an important goal. Here we report the synthesis of large-area monolayer and multilayer, particularly bilayer, graphene films on Cu-Ni alloy foils by chemical vapor deposition with methane and hydrogen gas as precursors. The dependence of the initial stages of graphene growth rate on the substrate grain orientation was observed for the first time by electron backscattered diffraction and scanning electron microscopy. The thickness and quality of the graphene and graphite films obtained on such Cu-Ni alloy foils could be controlled by varying the deposition temperature and cooling rate and were studied by optical microscopy, scanning electron microscopy, atomic force microscopy, and micro-Raman imaging spectroscopy. The optical and electrical properties of the graphene and graphite films were studied as a function of thickness.

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,

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

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.

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

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 residue. This work provides a route to enhancing the electrical properties of CVD-grown graphene even when it has a thin polymer coating.

Selective-area fluorination of graphene with fluoropolymer and laser irradiation

We have devised a method to selectively fluorinate graphene by irradiating fluoropolymer-covered graphene with a laser. This fluoropolymer produces active fluorine radicals under laser irradiation that react with graphene but only in the laser-irradiated region. The kinetics of C-F bond formation is dependent on both the laser power and fluoropolymer thickness, proving that fluorination occurs by the decomposition of the fluoropolymer. Fluorination leads to a dramatic increase in the resistance of the graphene while the basic skeletal structure of the carbon bonding network is maintained. Considering the simplicity of the fluorination process and that it allows patterning with a nontoxic fluoropolymer as a solid source, this method could find application to generate fluorinated graphene in graphene-based electronic devices such as for the electrical isolation of graphene.