Na Yeon Kim

Creating Pores on Graphene Platelets by Low-Temperature KOH Activation for Enhanced Electrochemical Performance.

KOH activation of microwave exfoliated graphite oxide (MEGO) is investigated in detail at temperatures of 450-550 °C. Out of the activation temperature range conventionally used for the preparation of activated carbons (>600 °C), the reaction between KOH and MEGO platelets at relatively low temperatures allows one to trace the structural transition from quasi-two-dimensional graphene platelets to three-dimensional porous carbon. In addition, it is found that nanometer-sized pores are created in the graphene platelets at the activation temperature of around 450 °C, leading to a carbon that maintains the platelet-like morphology, yet with a specific surface area much higher than MEGO (e.g., increased from 156 to 937 m(2) g(-1) ). Such a porous yet highly conducting carbon shows a largely enhanced electrochemical activity and thus improved electrochemical performance when being used as electrodes in supercapacitors. A specific capacitance of 265 F g(-1) (185 F cm(-3) ) is obtained at a current density of 1 A g(-1) in 6 m KOH electrolyte, which remains 223 F g(-1) (156 F cm(-3) ) at the current density of 10 A g(-1) .

Rupturing C60 Molecules into Graphene-Oxide-like Quantum Dots: Structure, Photoluminescence, and Catalytic Application

The large-scale synthesis of graphene-oxide-like quantum dots (GOLQDs) is reported by oxidizing C(60) molecules using a modified Hummers method with a yield of ≈25 wt% readily achieved. The GOLQDs are highly soluble in water and in addition to hexagons have other carbon rings in the structure. They have an average height of ≈1.2 nm and a diameter distribution of 0.6-2.2 nm after drying on substrates. First-principle calculations indicate that a possible rupturing route may include the insertion of oxygen atoms to CC bonds in the C(60) molecule, followed by rupture of that CC bonds. The GOLQD suspension has a strong photoluminescence (PL) with peak position dependent on excitation wavelength. The PL is related to the size and emissive traps caused by oxygen-containing groups. The GOLQDs also catalyze the oxidation of benzyl alcohol with a high selectivity.

Controlled Folding of Single Crystal Graphene

Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu(111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. By identifying the original lattice orientation of the monolayer graphene on Cu foil, or establishing the relation between the fold angle and twist angle, this folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two-dimensional nanomaterials.

Atomic Scale Study on Growth and Heteroepitaxy of ZnO Monolayer on Graphene

Atomically thin semiconducting oxide on graphene carries a unique combination of wide band gap, high charge carrier mobility, and optical transparency, which can be widely applied for optoelectronics. However, study on the epitaxial formation and properties of oxide monolayer on graphene remains unexplored due to hydrophobic graphene surface and limits of conventional bulk deposition technique. Here, we report atomic scale study of heteroepitaxial growth and relationship of a single-atom-thick ZnO layer on graphene using atomic layer deposition. We demonstrate atom-by-atom growth of zinc and oxygen at the preferential zigzag edge of a ZnO monolayer on graphene through in situ observation. We experimentally determine that the thinnest ZnO monolayer has a wide band gap (up to 4.0 eV), due to quantum confinement and graphene-like structure, and high optical transparency. This study can lead to a new class of atomically thin two-dimensional heterostructures of semiconducting oxides formed by highly controlled epitaxial growth.

Oxidation behavior of graphene-coated copper at intrinsic graphene defects of different origins

The development of ultrathin barrier films is vital to the advanced semiconductor industry. Graphene appears to hold promise as a protective coating; however, the polycrystalline and defective nature of engineered graphene hinders its practical applications. Here, we investigate the oxidation behavior of graphene-coated Cu foils at intrinsic graphene defects of different origins. Macro-scale information regarding the spatial distribution and oxidation resistance of various graphene defects is readily obtained using optical and electron microscopies after the hot-plate annealing. The controlled oxidation experiments reveal that the degree of structural deficiency is strongly dependent on the origins of the structural defects, the crystallographic orientations of the underlying Cu grains, the growth conditions of graphene, and the kinetics of the graphene growth. The obtained experimental and theoretical results show that oxygen radicals, decomposed from water molecules in ambient air, are effectively inverted at Stone–Wales defects into the graphene/Cu interface with the assistance of facilitators.Graphene holds promise as a protective coating; however, lattice defects may hinder its practical applicability. Here, the authors investigate the oxidation behavior of graphene-coated copper foils and unveil the interplay between structural defects and oxygen radicals from water molecules in ambient air.

Evidence of Local Commensurate State with Lattice Match of Graphene on Hexagonal Boron Nitride

Transition to a commensurate state changes the local symmetry periodicity on two-dimensional van der Waals superstructures, evoking distinctive properties far beyond individual layers. We investigate the morphology of moiré superstructures of graphene on hexagonal boron nitride (hBN) with a low twist angle (≈0°) through moiré fringe analyses with dark field transmission electron microscopy. The moiré fringes exhibit local variation, suggesting that the interaction between graphene and hBN depends on the stacking configuration and that local transition to the commensurate state occurs through the reduced crystalline mismatch (that is, by lattice stretching and twisting on the graphene lattices). This moiré superstructure analysis suggests an inventive method for studying the interaction between stacked van der Waals layers and for discerning the altered electronic and optical properties of graphene on hBN superstructures with a low twist angle, even at low magnification.

Line-defect mediated formation of hole and Mo clusters in monolayer molybdenum disulfide

The production of hole and Mo cluster by electron beam irradiation in molybdenum disulfide (MoS2), which consists of S-Mo-S layers, is monitored over time using atomic resolution transmission electron microscopy. S vacancies are firstly formed due to knocking off of S atoms and then line defects are induced due to accumulation of S vacancies in MoS2 sheet instead of forming a hole. The line defects tend to be merged at a point and a hole is formed subsequently at the point. Mo atoms tend to be clustered discretely as a nano sheet along the edge of the hole due to difference in displacement threshold energy between Mo and S atoms under electron irradiation. After Mo clusters are nearly separated from MoS2 sheet, the clusters are transformed into body-centered cubic nanocrystal of Mo during prolonged electron beam irradiation. The line defect mediated formation of hole and Mo cluster only occurs within a single grain of monolayer MoS2 sheet.

Unraveling the Water Impermeability Discrepancy in CVD-Grown Graphene

Graphene has recently attracted particular interest as a flexible barrier film preventing permeation of gases and moistures. However, it has been proved to be exceptionally challenging to develop large-scale graphene films with little oxygen and moisture permeation suitable for industrial uses, mainly due to the presence of nanometer-sized defects of obscure origins. Here, the origins of water permeable routes on graphene-coated Cu foils are investigated by observing the micrometer-sized rusts in the underlying Cu substrates, and a site-selective passivation method of the nanometer-sized routes is devised. It is revealed that nanometer-sized holes or cracks are primarily concentrated on graphene wrinkles rather than on other structural imperfections, resulting in severe degradation of its water impermeability. They are found to be predominantly induced by the delamination of graphene bound to Cu as a release of thermal stress during the cooling stage after graphene growth, especially at the intersection of the Cu step edges and wrinkles owing to their higher adhesion energy. Furthermore, the investigated routes are site-selectively passivated by an electron-beam-induced amorphous carbon layer, thus a substantial improvement in water impermeability is achieved. This approach is likely to be extended for offering novel barrier properties in flexible films based on graphene and on other atomic crystals.

A high-performance transparent graphene/vertically aligned carbon nanotube (VACNT) hybrid electrode for neural interfacing

Neural interfaces that do not damage cells or tissues are key to connecting brain functions to neural prosthetics. Here, we designed a transparent graphene/vertically aligned carbon nanotube (VACNT) electrode capable of extracellularly recording spontaneous action potentials in Sprague–Dawley rat primary cortex neurons. Graphene provided the dual function of contacting the VACNTs and visually monitoring the cell viability. The hybrid electrodes exhibited remarkably high peak-to-peak signal amplitudes (1600 μV) and low noise levels, presumably due to tight junction formation between the cells and the deformed CNTs. Spike simulation and high-resolution transmission electron microscopy (HRTEM) imaging confirmed the excellent interfacial characteristics of the cells and the transparent hybrid electrodes.

Epitaxial Growth of ZnO Monolayer on Graphene: The Thinnest Metal Oxide Semiconductor

Heteroepitaxial growth of metal oxide semiconductors on two-dimensional layered nanomaterials, combining wide band gap and high carrier density, has become a new integration method for fabricating electronic devices [1]. Among semiconductor materials, zinc oxide has been used in novel transparent electronic devices as forms of epitaxial layer on graphene [2, 3]. Thermodynamically, hexagonal wurtzite ZnO is the common form [2]. The wurtzite structure of ZnO can be transformed to a planar ZnO monolayer in which Zn and O atoms reside in a trigonal planar coordination, instead of the bulk tetrahedral configuration formed when ZnO is thinned down to a few atomic layers [4]. Since ZnO monolayers on graphene can have many applications in electronic devices, growth of thin ZnO layers on graphene has been studied extensively [5]. Here, we provide experimental evidence for the epitaxial growth of a ZnO monolayer on graphene using atomic resolution transmission electron microscopy along with the corresponding image simulations and first principles calculations. Furthermore, we demonstrate through in situ observation the atom-by-atom growth of zinc and oxygen at the zigzag edge of the ZnO monolayer on graphene. In addition, we demonstrate the presence of 2–3 nm quantum dots of the epitaxial ZnO monolayer grown by atomic layer deposition (ALD). Unlike conventional bulk ZnO, ZnO quantum dots have potential applications in nanoscale devices, such as photonic and electronic devices, due to the quantum confinement effect [6].