Atomically thin iridium nanosheets for oxygen evolution electrocatalysis.

2D nanostructures of noble metals hold great potential for developing efficient electrocatalysts due to their high atom efficiency associated with their large specific surface area and abundant active sites. Here, we introduce a one-pot solvothermal synthesis method that can enable the fabrication of freestanding atomically thin Ir nanosheets. The thermal decomposition of a complex of Ir and a long-chain amine, which could readily be formed with the assistance of a strong base, under CO flow conditions successfully yielded Ir nanosheets consisting of 2-4 atomic layers. The prepared Ir nanosheets showed prominent activity and stability toward oxygen evolution electrocatalysis in acidic conditions, which can be attributed to their ultrathin 2D structure.

A Modified Wet Transfer Method for Eliminating Interfacial Impurities in Graphene.

Graphene has immense potential as a material for electronic devices owing to its unique electrical properties. However, large-area graphene produced by chemical vapor deposition (CVD) must be transferred from the as-grown copper substrate to an arbitrary substrate for device fabrication. The conventional wet transfer technique, which uses FeCl3 as a Cu etchant, leaves microscale impurities from the substrate, and the etchant adheres to graphene, thereby degrading its electrical performance. To address this limitation, this study introduces a modified transfer process that utilizes a temporary UV-treated SiO2 substrate to adsorb impurities from graphene before transferring it onto the final substrate. Optical microscopy and Raman mapping confirmed the adhesion of impurities to the temporary substrate, leading to a clean graphene/substrate interface. The retransferred graphene shows a reduction in electron-hole asymmetry and sheet resistance compared to conventionally transferred graphene, as confirmed by the transmission line model (TLM) and Hall effect measurements (HEMs). These results indicate that only the substrate effects remain in action in the retransferred graphene, and most of the effects of the impurities are eliminated. Overall, the modified transfer process is a promising method for obtaining high-quality graphene suitable for industrial-scale utilization in electronic devices.

Charge Transport in UV-Oxidized Graphene and Its Dependence on the Extent of Oxidation.

Graphene oxides with different degrees of oxidation are prepared by controlling UV irradiation on graphene, and the charge transport and the evolution of the transport gap are investigated according to the extent of oxidation. With increasing oxygenous defect density nD, a transition from ballistic to diffusive conduction occurs at nD≃1012 cm-2 and the transport gap grows in proportion to nD. Considering the potential fluctuation related to the e-h puddle, the bandgap of graphene oxide is deduced to be Eg≃30nD(1012cm-2) meV. The temperature dependence of conductivity showed metal-insulator transitions at nD≃0.3×1012 cm-2, consistent with Ioffe-Regel criterion. For graphene oxides at nD≥4.9×1012 cm-2, analysis indicated charge transport occurred via 2D variable range hopping conduction between localized sp2 domain. Our work elucidates the transport mechanism at different extents of oxidation and supports the possibility of adjusting the bandgap with oxygen content.

All-Graphene-Contact Electrically Pumped On-Demand Transferrable Nanowire Source.

On-demand NW light sources in a photonic integrated circuit (PIC) have faced several practical challenges. Here, we report on an all-graphene-contact, electrically pumped, on-demand transferrable NW source that is fabricated by implementing an all-graphene-contact approach in combination with a highly accurate microtransfer printing technique. A vertically p-i-n-doped top-down-fabricated semiconductor NW with optical gain structures is electrically pumped through the patterned multilayered graphene contacts. Electroluminescence (EL) spectroscopy results reveal that the electrically driven NW device exhibits strong EL emission between the contacts and displays waveguiding properties. Further, a single NW device is precisely integrated into an existing photonic waveguide to perform light coupling and waveguiding experiments. Three-dimensional numerical simulation results show a good agreement with experimental observations. We believe that our all-graphene-contact approach is readily applicable to various micro/nanostructures and devices, which facilitates stable electrical operation and thus extends their practical applicability in compact integrated circuits.

Doping effect in graphene-graphene oxide interlayer.

Interlayer coupling in graphene-based van der Waals (vdW) heterostructures plays a key role in determining and modulating their physical properties. Hence, its influence on the optical and electronic properties cannot be overlooked in order to promote various next-generation applications in electronic and opto-electronic devices based on the low-dimensional materials. Herein, the optical and electrical properties of the vertically stacked large area heterostructure of the monolayer graphene transferred onto a monolayer graphene oxide film are investigated. An effective and stable p-doping property of this structure is shown by comparison to that of the graphene device fabricated on a silicon oxide substrate. Through Raman spectroscopy and density functional theory calculations of the charge transport characteristics, it is found that graphene is affected by sustainable p-doping effects induced from underneath graphene oxide even though they have weak interlayer interactions. This finding can facilitate the development of various fascinating graphene-based heterostructures and extend their practical applications in integrated devices with advanced functionalities.

Raman Spectra Shift of Few-Layer IV-VI 2D Materials.

Raman spectroscopy is the most commonly used method to investigate structures of materials. Recently, few-layered IV-VI 2D materials (SnS, SnSe, GeS, and GeSe) have been found and ignited significant interest in electronic and optical applications. However, unlike few-layer graphene, in which its interlayer structures such as the number of its layers are confirmed through measurement of the Raman scattering, few-layer IV-VI 2D materials have not yet been developed to the point of understanding their interlayer structure. Here we performed first-principles calculations on Raman spectroscopy for few-layer IV-VI 2D materials. In addition to achieving consistent results with measurements of bulk structures, we revealed significant red and blue shifts of characteristic Raman modes up to 100 cm-1 associated with the layer number. These shifts of lattice vibrational modes originate from the change of the bond lengths between the metal atoms and chalcogen atoms through the change of the interlayer interactions. Particularly, our study shows weak covalent bonding between interlayers, making the evolution of Raman signals according to the thickness different from other vdW materials. Our results suggest a new way for obtaining information of layer structure of few-layer IV-VI 2D materials through Raman spectroscopy.

PARP1 Inhibition as a Novel Therapeutic Target for Keloid Disease.

Objective: Inactivation of poly(ADP-ribose) polymerase 1 (PARP1) has been found to have protective effect in several fibrotic diseases. But the effect is not studied yet in keloids. Herein, we evaluated the therapeutic effect of PARP1 inhibitor, rucaparib, for keloids. Approach: The protein expressions of PARP1 and smad3 were evaluated with western blotting in keloids and controls. The effect of rucaparib was evaluated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay and migration assay. We further analyzed the effect of rucaparib on patient-derived keloid xenograft murine model. Results: The protein expressions of PARP1 and smad3 were significantly higher in keloid tissue. Rucaparib (20 µM) significantly suppressed the proliferation of keloid fibroblasts. Moreover, the combination of rucaparib (20 µM) and triamcinolone (50 µM) showed additive suppressive effect on keloid fibroblasts. Migration assay showed that rucaparib (10 µM) significantly suppressed the migration of keloid fibroblasts. Fibrosis markers in keloid fibroblasts significantly decreased after rucaparib treatment (20 µM). In patient-derived keloid xenograft model, rucaparib significantly reduced the size of keloid tissue. Innovation and Conclusion: The study data suggest PARP1 might be a novel therapeutic target for keloid disease. PARP1 inhibitor, rucaparib, might be a promising therapeutic drug for the treatment of keloid disease.

Gate-tuned conductance of graphene-ribbon junctions with nanoscale width variations.

To utilize graphene as interconnection electrodes in high-density nanoelectronic structures, the electrical stability of graphene should be guaranteed under nanometer-scale deviations. Graphene-ribbon (GR) junctions with accessible dimensions (i.e., sub-micrometer widths) are used in diverse interconnection electrode applications and should be characterized properly if they are to be applied in high-density nanoelectronics. Analyzing the effects of nanoscale GR width variations on the conductance of the entire graphene electrode is necessary for their proper characterization. Here, we diagnose the conductance and thermal effect of graphene electrode junctions constructed from GRs of various widths and directions under gate-tuned voltages. On applying partial gate voltages, we identify the effect of local potential variance on the entire graphene electrode junction. As a result, we were able to perceive precise and minute conductance variations for the entire graphene electrode, arising mainly from different sub-micrometer-scale widths of the GRs, which could not be distinguished using conventional global gating methods.

Layer number identification of CVD-grown multilayer graphene using Si peak analysis.

Since the successful exfoliation of graphene, various methodologies have been developed to identify the number of layers of exfoliated graphene. The optical contrast, Raman G-peak intensity, and 2D-peak line-shape are currently widely used as the first level of inspection for graphene samples. Although the combination analysis of G- and 2D-peaks is powerful for exfoliated graphene samples, its use is limited in chemical vapor deposition (CVD)-grown graphene because CVD-grown graphene consists of various domains with randomly rotated crystallographic axes between layers, which makes the G- and 2D-peaks analysis difficult for use in number identification. We report herein that the Raman Si-peak intensity can be a universal measure for the number identification of multilayered graphene. We synthesized a few-layered graphene via the CVD method and performed Raman spectroscopy. Moreover, we measured the Si-peak intensities from various individual graphene domains and correlated them with the corresponding layer numbers. We then compared the normalized Si-peak intensity of the CVD-grown multilayer graphene with the exfoliated multilayer graphene as a reference and successfully identified the layer number of the CVD-grown graphene. We believe that this Si-peak analysis can be further applied to various 2-dimensional (2D) materials prepared by both exfoliation and chemical growth.

Gas molecule sensing of van der Waals tunnel field effect transistors.

van der Waals (vdW) heterostructures with two-dimensional (2D) crystals such as graphene, hexagonal boron nitride (hBN) and transition metal dichalcogenides (TMDCs) allow us to demonstrate atomically thin field-effect transistors (FETs), photodetectors (PDs) and photovoltaic devices capable of higher performance and greater stability levels than conventional devices. Although there have been studies of gas molecule sensing with 2D crystal channels, vdW heterostructures based on 2D crystals have not been employed thus far. Here, utilizing graphene/WS2/graphene (G/WS2/G) vdW heterostructure tunnel FETs, we demonstrate the rectification behavior of the sensitivity signal by tuning the WS2 potential barriers as a function of the gas molecule concentration and devise a fingerprint map of the sensitivity variation corresponding to an individual ratio of two different molecules in a gas mixture. Because the separation of different gas molecule concentrations from gas mixtures is in high demand in the gas-sensing research field, this result will greatly assist in the progress on selective gas sensing.

Spatially localized wavelength-selective absorption in morphology-modulated semiconductor nanowires.

In this study, we proposed morphology-modulated Si nanowires (NWs) with a hexagonal cross-section and numerically investigated their resonant optical absorption and scattering properties. The calculated absorption and scattering efficiency spectra of the NWs exhibited optical resonances that could be controlled by tuning the aspect ratio (AR) of the NW cross-sectional shapes. The spectra also revealed interesting spectral behaviors including resonant peak shifts in the absorption spectrum and asymmetric line shapes in the scattering spectrum. To achieve spatially confined and wavelength-selective light absorption, we periodically modulated the geometry of the diameter in a single NW by combining two different ARs; we call these "diameter-modulated NWs." We designed various diameter-modulated NWs with short and long pitch sizes, and we observed unique and interesting features in the optical resonance and corresponding light absorption spectra such as grating modes and three-dimensional cavity modes. The proposed diameter-modulated NWs can be promising building blocks for the nanoscale localized light absorption and detection in compact nanophotonic integrated circuits.

Enhancement of Friction by Water Intercalated between Graphene and Mica.

Common experience shows that friction converts mechanical energy into heat. The first part of this process is vibrational excitation of atoms at the interface between rubbing bodies. The second part is the removal of the vibration energy by transferring it from the interface to the substrate. However, it is difficult to disentangle the excitation and energy transfer processes. We solved this by using a system consisting of a SiO2-terminated tip sliding over graphene deposited on mica with intercalated water between them. The intercalated water was found to increase friction by a factor of ∼3 relative to dry mica. Density functional theory calculations show that water broadens the spectral range of graphene vibrations-particularly the low-frequency flexural modes-thus providing new excitation channels and also by increasing the overlap with the atomic vibrations of the mica substrate, which facilitates coupling and energy transfer.

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.

Charge transport-driven selective oxidation of graphene.

Due to the tunability of the physical, electrical, and optical characteristics of graphene, precisely controlling graphene oxidation is of great importance for potential applications of graphene-based electronics. Here, we demonstrate a facile and precise way for graphene oxidation controlled by photoexcited charge transfer depending on the substrate and bias voltage. It is observed that graphene on TiO2 is easily oxidized under UV-ozone treatment, while graphene on SiO2 remains unchanged. The mechanism for the selective oxidation of graphene on TiO2 is associated with charge transfer from the TiO2 to the graphene. Raman spectra were used to investigate the graphene following applied bias voltages on the graphene/TiO2 diode under UV-ozone exposure. We found that under a reverse bias of 0.6 V on the graphene/TiO2 diode, graphene oxidation was accelerated under UV-ozone exposure, thus confirming the role of charge transfer between the graphene and the TiO2 that results in the selective oxidation of the graphene. The selective oxidation of graphene can be utilized for the precise, nanoscale patterning of the graphene oxide and locally patterned chemical doping, finally leading to the feasibility and expansion of a variety of graphene-based applications.

Facile fabrication of properties-controllable graphene sheet.

Graphene has been received a considerable amount of attention as a transparent conducting electrode (TCE) which may be able to replace indium tin oxide (ITO) to overcome the significant weakness of the poor flexibility of ITO. Given that graphene is the thinnest 2-dimensional (2D) material known, it shows extremely high flexibility, and its lateral periodic honeycomb structure of sp(2)-bonded carbon atoms enables ~2.3% of incident light absorption per layer. However, there is a trade-off between the electrical resistance and the optical transmittance, and the fixed absorption rate in graphene limits is use when fabricating devices. Therefore, a more efficient method which continuously controls the optical and electrical properties of graphene is needed. Here, we introduce a method which controls the optical transmittance and the electrical resistance of graphene through various thicknesses of the top Cu layers with a Cu/Ni metal catalyst structure used to fabricate a planar mesh pattern of single and multi-layer graphene. We exhibit a continuous transmittance change from 85% (MLG) to 97.6% (SLG) at an incident light wavelength of 550 nm on graphene samples simultaneously grown in a CVD quartz tube. We also investigate the relationships between the sheet resistances.

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 graphene's 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.

Effects of donor age, long-term passage culture, and cryopreservation on tonsil-derived mesenchymal stem cells.

OBJECTIVES: Human mesenchymal stem cells (MSCs) are efficacious in various cellular therapeutic applications and have been isolated from several tissues. Recent studies have reported that human tonsil tissue contains a new source of progenitor cells, potentially applicable for cell-based therapies. Information about the effects of donor age, long-term passage and cryopreservation are essential for clinical applications and cell-based therapies. Therefore, the authors investigated how the morphology, cell-surface markers, proliferation potential and differentiation capacity of tonsil-derived MSCs (T-MSCs) were affected by donor age, long-term passage, and cryopreservation. MATERIALS AND METHODS: T-MSCs were isolated from tonsillar tissue of 20 patients undergoing tonsillectomy. Authors evaluated the effects of donor-age, long-term passage, and cryopreservation on the morphology, surface markers, proliferation potential and differentiation capacities of T-MSCs. RESULTS: T-MSCs exhibited a fibroblast-like, spindle-shaped appearance. There were no significant morphological differences according to donor age, long-term passage or cryopreservation. T-MSCs isolated from donors of various ages were positive for markers CD90, CD44, and CD73, but negative for CD45, CD31, and HLA-DR. There were no significant differences in the expression of positive and negative surface markers as a function of donor age, long-term passage and cryopreservation. T-MSCs from different donor age groups showed similar proliferation potentials after passage 2. After long-term passage and cryopreservation, there were no significant morphological differences. Cryopreservation did not affect the proliferation potential of T-MSCs, but there was a significant decrease in the proliferation potential in long-term passage T-MSCs (passage 15). The effect of donor age, long-term passage and cryopreservation on the in vitro adipogenic, osteogenic, and chondrogenic differentiation potential of T-MSCs was not significant. CONCLUSION: The effect of donor age, long-term passage culture, and cryopreservation on T-MSC properties are negligible, except for the proliferation capacity of long-term cultured T-MSCs. Therefore, T-MSCs are considered to be promising MSCs that can be used as future alternative sources for autologous or allogenic MSCs.

Configuration of ripple domains and their topological defects formed under local mechanical stress on hexagonal monolayer graphene.

Ripples in graphene are extensively investigated because they ensure the mechanical stability of two-dimensional graphene and affect its electronic properties. They arise from spontaneous symmetry breaking and are usually manifested in the form of domains with long-range order. It is expected that topological defects accompany a material exhibiting long-range order, whose functionality depends on characteristics of domains and topological defects. However, there remains a lack of understanding regarding ripple domains and their topological defects formed on monolayer graphene. Here we explore configuration of ripple domains and their topological defects in exfoliated monolayer graphenes on SiO2/Si substrates using transverse shear microscope. We observe three-color domains with three different ripple directions, which meet at a core. Furthermore, the closed domain is surrounded by an even number of cores connected together by domain boundaries, similar to topological vortex and anti-vortex pairs. In addition, we have found that axisymmetric three-color domains can be induced around nanoparticles underneath the graphene. This fascinating configuration of ripple domains may result from the intrinsic hexagonal symmetry of two-dimensional graphene, which is supported by theoretical simulation using molecular dynamics. Our findings are expected to play a key role in understanding of ripple physics in graphene and other two-dimensional materials.

Correlation between micrometer-scale ripple alignment and atomic-scale crystallographic orientation of monolayer graphene.

Deformation normal to the surface is intrinsic in two-dimensional materials due to phononic thermal fluctuations at finite temperatures. Graphene's negative thermal expansion coefficient is generally explained by such an intrinsic property. Recently, friction measurements on graphene exfoliated on a silicon oxide surface revealed an anomalous anisotropy whose origin was believed to be the formation of ripple domains. Here, we uncover the atomistic origin of the observed friction domains using a cantilever torsion microscopy in conjunction with angle-resolved photoemission spectroscopy. We experimentally demonstrate that ripples on graphene are formed along the zigzag direction of the hexagonal lattice. The formation of zigzag directional ripple is consistent with our theoretical model that takes account of the atomic-scale bending stiffness of carbon-carbon bonds and the interaction of graphene with the substrate. The correlation between micrometer-scale ripple alignment and atomic-scale arrangement of exfoliated monolayer graphene is first discovered and suggests a practical tool for measuring lattice orientation of graphene.

Controlled mechnical modification of manganite surface with nanoscale resolution.

We investigated the surfaces of magnetoresistive manganites, La(1-x)Ca(x)MnO3 and La(2-2x)Sr(1+2x)Mn2O7, using a combination of ultrahigh vacuum conductive, electrostatic and magnetic force microscopy methods. Scanning as-grown film with a metal tip, even with zero applied bias, was found to modify the surface electronic properties such that in subsequent scans, the conductivity is reduced below the noise level of conductive probe microscopy. Scanned areas also reveal a reduced contact potential difference relative to the pristine surface by ∼0.3 eV. We propose that contact-pressure of the tip modifies the electrochemical potential of oxygen vacancies via the Vegard effect, causing vacancy motion and concomitant changes of the electronic properties.