Seung Jin Chae

Influence of Copper Morphology in Forming Nucleation Seeds for Graphene Growth

We report that highly crystalline graphene can be obtained from well-controlled surface morphology of the copper substrate. Flat copper surface was prepared by using a chemical mechanical polishing method. At early growth stage, the density of graphene nucleation seeds from polished Cu film was much lower and the domain sizes of graphene flakes were larger than those from unpolished Cu film. At later growth stage, these domains were stitched together to form monolayer graphene, where the orientation of each domain crystal was unexpectedly not much different from each other. We also found that grain boundaries and intentionally formed scratched area play an important role for nucleation seeds. Although the best monolayer graphene was grown from polished Cu with a low sheet resistance of 260 Ω/sq, a small portion of multilayers were also formed near the impurity particles or locally protruded parts.

Probing graphene grain boundaries with optical microscopy

Grain boundaries in graphene are formed by the joining of islands during the initial growth stage, and these boundaries govern transport properties and related device performance. Although information on the atomic rearrangement at graphene grain boundaries can be obtained using transmission electron microscopy and scanning tunnelling microscopy, large-scale information regarding the distribution of graphene grain boundaries is not easily accessible. Here we use optical microscopy to observe the grain boundaries of large-area graphene (grown on copper foil) directly, without transfer of the graphene. This imaging technique was realized by selectively oxidizing the underlying copper foil through graphene grain boundaries functionalized with O and OH radicals generated by ultraviolet irradiation under moisture-rich ambient conditions: selective diffusion of oxygen radicals through OH-functionalized defect sites was demonstrated by density functional calculations. The sheet resistance of large-area graphene decreased as the graphene grain sizes increased, but no strong correlation with the grain size of the copper was revealed, in contrast to a previous report. Furthermore, the influence of graphene grain boundaries on crack propagation (initialized by bending) and termination was clearly visualized using our technique. Our approach can be used as a simple protocol for evaluating the grain boundaries of other two-dimensional layered structures, such as boron nitride and exfoliated clays.

Fully Rollable Transparent Nanogenerators Based on Graphene Electrodes

[*] Prof. S.-W. Kim, H.-K. Park, J.-S. Seo School of Advanced Materials Science and Engineering SKKU Advanced Institute of Nanotechnology (SAINT) Center for Human Interface Nanotechnology (HINT) Sungkyunkwan University Suwon, 440-746 (Republic of Korea) E-mail: kimsw1@skku.edu Dr. J.-Y. Choi, Dr. D. Choi, Dr. W. M. Choi, H.-J. Shin, Dr. J. Park, S.-M. Yoon, Dr. S. Y. Lee, Dr. J. M. Kim Samsung Advanced Institute of Technology Yongin, Gyeonggi, 446-712 (Republic of Korea) E-mail: jaeyoung88.choi@samsung.com M.-Y. Choi School of Advanced Materials and System Engineering Kumoh National Institute of Technology Gumi, Gyeongbuk, 730-701 (Republic of Korea)

Layer-by-layer doping of few-layer graphene film.

We propose a new method of layer-by-layer (LbL) doping of thin graphene films. Large area monolayer graphene was synthesized on Cu foil by using the chemical vapor deposition method. Each layer was transferred on a polyethylene terephthalate substrate followed by a salt-solution casting, where the whole process was repeated several times to get LbL-doped thin layers. With this method, sheet resistance was significantly decreased up to approximately 80% with little sacrifice in transmittance. Unlike samples fabricated by topmost layer doping, our sample shows better environmental stability due to the presence of dominant neutral Au atoms on the surface which was confirmed by angle-resolved X-ray photoelectron spectroscopy. The sheet resistance of the LbL-doped four-layer graphene (11 x 11 cm(2)) was 54 Omega/sq at 85% transmittance, which meets the technical target for industrial applications.

Diffusion Mechanism of Lithium Ion through Basal Plane of Layered Graphene

Coexistence of both edge plane and basal plane in graphite often hinders the understanding of lithium ion diffusion mechanism. In this report, two types of graphene samples were prepared by chemical vapor deposition (CVD): (i) well-defined basal plane graphene grown on Cu foil and (ii) edge plane-enriched graphene layers grown on Ni film. Electrochemical performance of the graphene electrode can be split into two regimes depending on the number of graphene layers: (i) the corrosion-dominant regime and (ii) the lithiation-dominant regime. Li ion diffusion perpendicular to the basal plane of graphene is facilitated by defects, whereas diffusion parallel to the plane is limited by the steric hindrance that originates from aggregated Li ions adsorbed on the abundant defect sites. The critical layer thickness (l(c)) to effectively prohibit substrate reaction using CVD-grown graphene layers was predicted to be ∼6 layers, independent of defect population. Our density functional theory calculations demonstrate that divacancies and higher order defects have reasonable diffusion barrier heights allowing lithium diffusion through the basal plane but neither monovacancies nor Stone-Wales defect.

Controlled Growth of Semiconducting Nanowire, Nanowall, and Hybrid Nanostructures on Graphene for Piezoelectric Nanogenerators

Precise control of morphologies of one- or two-dimensional nanostructures during growth has not been easy, usually degrading device performance and therefore limiting applications to various advanced nanoscale electronics and optoelectronics. Graphene could be a platform to serve as a substrate for both morphology control and direct use of electrodes due to its ideal monolayer flatness with π electrons. Here, we report that, by using graphene directly as a substrate, vertically well-aligned zinc oxide (ZnO) nanowires and nanowalls were obtained systematically by controlling gold (Au) catalyst thickness and growth time without inflicting significant thermal damage on the graphene layer during thermal chemical vapor deposition of ZnO at high temperature of about 900 °C. We clarify Au nanoparticle positions at graphene-ZnO heterojunctions that are very important in realizing advanced nanoscale electronic and optoelectronic applications of such nanostructures. Further, we demonstrate a piezoelectric nanogenerator that was fabricated from the vertically aligned nanowire-nanowall ZnO hybrid/graphene structure generates a new type of direct current through the specific electron dynamics in the nanowire-nanowall hybrid.

Gate-Controlled Nonlinear Conductivity of Dirac Fermion in Graphene Field-Effect Transistors Measured by Terahertz Time-Domain Spectroscopy

We present terahertz spectroscopic measurements of Dirac fermion dynamics from a large-scale graphene that was grown by chemical vapor deposition and on which carrier density was modulated by electrostatic and chemical doping. The measured frequency-dependent optical sheet conductivity of graphene shows electron-density-dependence characteristics, which can be understood by a simple Drude model. In a low carrier density regime, the optical sheet conductivity of graphene is constant regardless of the applied gate voltage, but in a high carrier density regime, it has nonlinear behavior with respect to the applied gate voltage. Chemical doping using viologen was found to be efficient in controlling the equilibrium Fermi level without sacrificing the unique carrier dynamics of graphene.

Role of anions in the AuCl3-doping of carbon nanotubes.

The doping/dedoping mechanism of carbon nanotubes (CNTs) with AuCl(3) has been investigated with regard to the roles of cations and anions. Contrary to the general belief that CNTs are p-doped through the reduction of cationic Au(3+) to Au(0), we observed that chlorine anions play a more important role than Au cations in doping. To estimate the effects of Cl and Au on CNTs, the CNT film was dedoped as a function of the annealing temperature (100-700 °C) under an Ar ambient and was confirmed by the sheet resistance change and the presence of a G-band in the Raman spectra. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the doping level of the CNT film was strongly related to the amount of adsorbed chlorine atoms. Annealing at temperatures up to 200 °C did not change the amount of adsorbed Cl atoms on the CNTs, and the CNT film was stable under ambient conditions. Alternatively, Cl atoms started to dissociate from CNTs at 300 °C, and the stability of the film was degraded. Furthermore, the change in the amount of Cl atoms in CNTs was inversely proportional to the change in the sheet resistance. Our observations of the Cl adsorption, either directly or mediated by an Au precursor on the CNT surface, are congruent with the previous theoretical prediction.

Transfer‐Free Growth of Few‐Layer Graphene by Self‐Assembled Monolayers

Graphene is an ideal 2D planar structure with an electron mobility that reaches 200 000 cm 2 V − 1 s − 1 , an ideal theoretical sheet resistance of 30 Ω sq − 1 , and an excellent transmittance of 97.5% per layer. [ 1–3 ] Recent development of large area graphene synthesis on a metal layer by chemical vapor deposition opened the possibility for a wide range of applications. [ 4–8 ] Although a Ni metal layer provided an effi cient way of producing graphene, controlling the number of layers has not been realized and the graphene layers are not uniform. [ 4–6 ] Cu foil has been used to produce monolayer graphene by the self-limiting growth but controlling the number of graphene layers has never been accessible. [ 8 ] However, controlling the number of graphene layers with high uniformity is a prerequisite for numerous applications. For instance, the bandgap is opened in bilayer graphene, which is useful for transistors. [ 9 ] Furthermore, these growth methods on a metal layer involve an inevitable transfer step of large area graphene that creates defects, impurities, wrinkles, and cracks and has been a bottleneck for science and technology innovation. [ 10 ]

Graphene/carbon nanotube hybrid-based transparent 2D optical array.

Graphene/carbon nanotube (CNT) hybrid structures are fabricated for use as optical arrays. Vertically aligned CNTs are directly synthesized on a graphene/quartz substrate using plasma-enhanced chemical vapor deposition (PECVD). Graphene preserves the transparency and resistance during CNT growth. Highly aligned single-walled CNTs show a better performance for the diffraction intensity.