Jin Sik Choi

Interference effect on Raman spectrum of graphene on SiO 2 / Si

The intensity ratio between two major Raman bands in graphene is one of the most important information for physics of graphene and has been believed to represent various intrinsic properties of graphene without critical assessment of extrinsic effects. We report a micro Raman spectroscopy study on the Raman intensity ratio of the 2D band to the G Raman band of graphene varying the thickness of dielectric layers (SiO_2) underneath it. The ratio is shown to change by almost 370% when the thickness is varied by 60%. The large variation in the ratio is well explained by theoretical calculations considering multiple Raman scattering events at the interfaces. Our analysis shows that the interference effect is critical in extracting the intrinsic 2D to G intensity ratio and therefore must be taken into account in extracting various physical properties of graphene from Raman measurements.

Friction Anisotropy–Driven Domain Imaging on Exfoliated Monolayer Graphene

Otherwise identical regions of supported graphene can be distinguished by changes in friction with sliding direction. Graphene produced by exfoliation has not been able to provide an ideal graphene with performance comparable to that predicted by theory, and structural and/or electronic defects have been proposed as one cause of reduced performance. We report the observation of domains on exfoliated monolayer graphene that differ by their friction characteristics, as measured by friction force microscopy. Angle-dependent scanning revealed friction anisotropy with a periodicity of 180° on each friction domain. The friction anisotropy decreased as the applied load increased. We propose that the domains arise from ripple distortions that give rise to anisotropic friction in each domain as a result of the anisotropic puckering of the graphene.

Nanoscale Lithography on Monolayer Graphene Using Hydrogenation and Oxidation

Monolayer graphene is one of the most interesting materials applicable to next-generation electronic devices due to its transport properties. However, realization of graphene devices requires suitable nanoscale lithography as well as a method to open a band gap in monolayer graphene. Nanoscale hydrogenation and oxidation are promising methods to open an energy band gap by modification of surface structures and to fabricate nanostructures such as graphene nanoribbons (GNRs). Until now it has been difficult to fabricate nanoscale devices consisting of both hydrogenated and oxidized graphene because the hydrogenation of graphene requires a complicated process composed of large-scale chemical modification, nanoscale patterning, and etching. We report on nanoscale hydrogenation and oxidation of graphene under normal atmospheric conditions and at room temperature without etching, wet process, or even any gas treatment by controlling just an external bias through atomic force microscope lithography. Both the lithographically defined nanoscale hydrogenation and oxidation have been confirmed by micro-Raman spectroscopy measurements. Patterned hydrogenated and oxidized graphene show insulating behaviors, and their friction values are several times larger than those of graphene. These differences can be used for fabricating electronic or electromechanical devices based on graphene.

Flexible and Transparent Gas Molecule Sensor Integrated with Sensing and Heating Graphene Layers

Graphene leading to high surface-to-volume ratio and outstanding conductivity is applied for gas molecule sensing with fully utilizing its unique transparent and flexible functionalities which cannot be expected from solid-state gas sensors. In order to attain a fast response and rapid recovering time, the flexible sensors also require integrated flexible and transparent heaters. Here, large-scale flexible and transparent gas molecule sensor devices, integrated with a graphene sensing channel and a graphene transparent heater for fast recovering operation, are demonstrated. This combined all-graphene device structure enables an overall device optical transmittance that exceeds 90% and reliable sensing performance with a bending strain of less than 1.4%. In particular, it is possible to classify the fast (≈14 s) and slow (≈95 s) response due to sp(2) -carbon bonding and disorders on graphene and the self-integrated graphene heater leads to the rapid recovery (≈11 s) of a 2 cm × 2 cm sized sensor with reproducible sensing cycles, including full recovery steps without significant signal degradation under exposure to NO2 gas.

Characteristics and Effects of Diffused Water Between Graphene and a SiO 2 Substrate

AbstractThe graphene/SiO2 system is a promising building block for next-generation electronic devices, integrating the high electromagnetic performance of graphene with the mature technology of Si-based electronic devices. It is well known that the electromagnetic performance of graphene/SiO2 is dramatically reduced by structural defects, such as wrinkles and folding, which are suspected to result from water droplets. Therefore, understanding water diffusion between graphene and SiO2 is required for controlling structural defects and thus improving the electromagnetic performance of this system. Although the behavior of water between graphene and atomically flat mica has been investigated, the characteristics and effects of diffused water between graphene and SiO2 remain unidentified. We have investigated water diffusion between monolayer graphene and SiO2 under high humidity conditions using atomic force microscopy. For a relative humidity of over 90%, water diffuses into graphene/SiO2 and forms an ice-like structure up to two layers thick. Liquid-like water can further diffuse in, stacking over the ice-like layer and evaporating relatively easily in the air causing graphene to wrinkle and fold. By similarly investigating water diffusion between graphene and mica, we argue that water-induced wrinkle formation depends on the hydrophilicity and roughness of the substrate.

Between Scylla and Charybdis: Hydrophobic Graphene-Guided Water Diffusion on Hydrophilic Substrates

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed.

Graphene–Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction

Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphenes unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports.

Memristor Behaviors of Highly Oriented Anatase TiO2 Film Sandwiched between Top Pt and Bottom SrRuO3 Electrodes

Bipolar resistive switching behaviors have been observed in Pt/TiO2/SrRuO3 structures whose TiO2 has a highly oriented anatase phase. The resistive switching behaviors reveal a strong dependence on the duration time of the switching pulse, top electrode size, and amplitude of the switching voltage. We have also analyzed the conduction mechanisms of each resistance state in both polarities. All the resistive switching characteristics of our Pt/TiO2/SrRuO3 structures can be explained by memristor behavior based on locally induced ion migration.

Facile characterization of ripple domains on exfoliated graphene

Ripples in graphene monolayers deposited on SiO(2)/Si wafer substrates were recently shown to give rise to friction anisotropy. High friction appears when the AFM tip slides in a direction perpendicular to the ripple crests and low friction when parallel. The direction of the ripple crest is, however, hard to determine as it is not visible in topographic images and requires elaborate measurements of friction as a function of angle. Here we report a simple method to characterize ripple crests by measuring the cantilever torsion signal while scanning in the non-conventional longitudinal direction (i.e., along the cantilever axis, as opposed to the usual friction measurement). The longitudinal torsion signal provides a much clearer ripple domain contrast than the conventional friction signal, while both signals show respective rotation angle dependences that can be explained using the torsion component of the normal reaction force exerted by the graphene ripples. We can also determine the ripple direction by comparing the contrast in torsion images obtained in longitudinal and lateral scans without sample rotation or complicated normalization.

Hot carrier multiplication on graphene/TiO2 Schottky nanodiodes.

Carrier multiplication (i.e. generation of multiple electron–hole pairs from a single high-energy electron, CM) in graphene has been extensively studied both theoretically and experimentally, but direct application of hot carrier multiplication in graphene has not been reported. Here, taking advantage of efficient CM in graphene, we fabricated graphene/TiO2 Schottky nanodiodes and found CM-driven enhancement of quantum efficiency. The unusual photocurrent behavior was observed and directly compared with Fowler’s law for photoemission on metals. The Fowler’s law exponent for the graphene-based nanodiode is almost twice that of a thin gold film based diode; the graphene-based nanodiode also has a weak dependence on light intensity—both are significant evidence for CM in graphene. Furthermore, doping in graphene significantly modifies the quantum efficiency by changing the Schottky barrier. The CM phenomenon observed on the graphene/TiO2 nanodiodes can lead to intriguing applications of viable graphene-based light harvesting.