Jin Hyoun Kang

One‐Step Synthesis of N‐doped Graphene Quantum Sheets from Monolayer Graphene by Nitrogen Plasma

High-quality N-doped graphene quantum sheets are successfully fabricated from as-grown monolayer graphene on Cu using nitrogen plasma, which can be transferred as a film-like layer or easily dispersed in an organic solvent for further optoelectronic or photoelectrochemical applications.

N-doped graphene quantum sheets on silicon nanowire photocathodes for hydrogen production

Photoelectrochemical hydrogen production from solar energy has been attracting much attention in the field of renewable energy technology. The realization of cost-effective hydrogen production by water splitting requires electrolysis or photoelectrochemical cells decorated with highly efficient co-catalysts. A critical requirement for catalysts in photoelectrochemical cells is not only the ability to boost the kinetics of a chemical reaction but also to exhibit durability against electrochemical and photoinduced degradation. In the race to replace previous noble-metal catalysts, the design of carbon-based catalysts represents an important research direction in the search for non-precious, environmentally benign, and corrosion-resistant catalysts. Herein, we suggest graphene quantum sheets as a catalyst for the solar-driven hydrogen evolution reaction on Si nanowire photocathodes. The optimum nanostructures of the Si photocathodes exhibit an enhanced photocurrent and a lower overpotential compared to those of a planar Si surface. This significant enhancement demonstrates how graphene quantum sheet catalysts can be used to produce Si nanowire photocathodes as hydrogen evolution reaction catalysts with high activity.

Vapor-phase molecular doping of graphene for high-performance transparent electrodes.

Doping is an essential process to engineer the conductivity and work-function of graphene for higher performance optoelectronic devices, which includes substitutional atomic doping by reactive gases, electrical/electrochemical doping by gate bias, and chemical doping by acids or reducing/oxidizing agents. Among these, the chemical doping has been widely used due to its simple process and high doping strength. However, it also has an instability problem in that the molecular dopants tend to gradually evaporate from the surface of graphene, leading to substantial decrease in doping effect with time. In particular, the instability problem is more serious for n-doped graphene because of undesirable reaction between dopants and oxygen or water in air. Here we report a simple method to tune the electrical properties of CVD graphene through n-doping by vaporized molecules at 70 °C, where the dopants in vapor phase are mildly adsorbed on graphene surface without direct contact with solution. To investigate the dependence on functional groups and molecular weights, we selected a series of ethylene amines as a model system, including ethylene diamine (EDA), diethylene triamine (DETA), and triethylene tetramine (TETA) with increasing number of amine groups showing different vapor pressures. We confirmed that the vapor-phase doping provides not only very high carrier concentration but also good long-term stability in air, which is particularly important for practical applications.

Exfoliation and Raman Spectroscopic Fingerprint of Few-Layer NiPS3 Van der Waals Crystals

The range of mechanically cleavable Van der Waals crystals covers materials with diverse physical and chemical properties. However, very few of these materials exhibit magnetism or magnetic order, and thus the provision of cleavable magnetic compounds would supply invaluable building blocks for the design of heterostructures assembled from Van der Waals crystals. Here we report the first successful isolation of monolayer and few-layer samples of the compound nickel phosphorus trisulfide (NiPS3) by mechanical exfoliation. This material belongs to the class of transition metal phosphorus trisulfides (MPS3), several of which exhibit antiferromagnetic order at low temperature, and which have not been reported in the form of ultrathin sheets so far. We establish layer numbers by optical bright field microscopy and atomic force microscopy, and perform a detailed Raman spectroscopic characterization of bilayer and thicker NiPS3 flakes. Raman spectral features are strong functions of excitation wavelength and sample thickness, highlighting the important role of interlayer coupling. Furthermore, our observations provide a spectral fingerprint for distinct layer numbers, allowing us to establish a sensitive and convenient means for layer number determination.

Growth dynamics and gas transport mechanism of nanobubbles in graphene liquid cells

Formation, evolution and vanishing of bubbles are common phenomena in nature, which can be easily observed in boiling or falling water, carbonated drinks, gas-forming electrochemical reactions and so on. However, the morphology and the growth dynamics of the bubbles at nanoscale have not been fully investigated owing to the lack of proper imaging tools that can visualize nanoscale objects in the liquid phase. Here, we demonstrate for the first time that the nanobubbles in water encapsulated by graphene membrane can be visualized by in-situ ultra-high vacuum transmission electron microscopy. Our microscopic results indicate two distinct growth mechanisms of merging nanobubbles and the existence of a critical radius of nanobubbles that determines the unusually long stability of nanobubbles. Interestingly, the gas transport through ultrathin water membranes at nanobubble interface is free from dissolution, which is clearly different from conventional gas transport that includes condensation, transmission and evaporation.

Strain Relaxation of Graphene Layers by Cu Surface Roughening

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.

Correction: N-doped graphene quantum sheets on silicon nanowire photocathodes for hydrogen production

Correction for ‘N-doped graphene quantum sheets on silicon nanowire photocathodes for hydrogen production’ by Uk Sim et al., Energy Environ. Sci., 2015, DOI: 10.1039/c4ee03607g.

Graphene oxide catalyzed cis-trans isomerization of azobenzene

We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO), where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

High-Density Single-Layer Coating of Gold Nanoparticles onto Multiple Substrates by Using an Intrinsically Disordered Protein of α-Synuclein for Nanoapplications

Functional graffiti of nanoparticles onto target surface is an important issue in the development of nanodevices. A general strategy has been introduced here to decorate chemically diverse substrates with gold nanoparticles (AuNPs) in the form of a close-packed single layer by using an omni-adhesive protein of α-synuclein (αS) as conjugated with the particles. Since the adsorption was highly sensitive to pH, the amino acid sequence of αS exposed from the conjugates and its conformationally disordered state capable of exhibiting structural plasticity are considered to be responsible for the single-layer coating over diverse surfaces. Merited by the simple solution-based adsorption procedure, the particles have been imprinted to various geometric shapes in 2-D and physically inaccessible surfaces of 3-D objects. The αS-encapsulated AuNPs to form a high-density single-layer coat has been employed in the development of nonvolatile memory, fule-cell, solar-cell, and cell-culture platform, where the outlying αS has played versatile roles such as a dielectric layer for charge retention, a sacrificial layer to expose AuNPs for chemical catalysis, a reaction center for silicification, and biointerface for cell attachment, respectively. Multiple utilizations of the αS-based hybrid NPs, therefore, could offer great versatility to fabricate a variety of NP-integrated advanced materials which would serve as an indispensable component for widespread applications of high-performance nanodevices.