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Transition metal dichalcogenides (TMDs) are promising candidates for the semiconductor industry owing to their superior electrical properties.

Summary The electrosynthesis of H2O2 via the 2e− oxygen reduction reaction (ORR) is an attractive method for the clean and continuous on-site production of H2O2, for which the development of active and selective electrocatalysts remains a significant challenge. Although carbon nanomaterials have demonstrated promising performance for H2O2 production, the lack of understanding of the active sites and key structural factors has impeded their development. In this work, we have prepared carbon-based model catalysts to investigate the active oxygen functional groups and structural factor. We have identified that the carboxyl group at the edge sites of graphitic carbons is the major active site for the 2e− ORR, and the carbonyl group is a secondary active site. The nanoporous carbon catalyst with abundant active edge sites and optimized structure exhibited the highest H2O2 electrosynthesis activity among the carbon-based catalysts reported to date and excellent long-term stability (168 h) with 99% H2O2 faradic efficiency.

In the last few decades, numerous studies have focused on designing suitable hydrophilic materials to inhibit surface-induced fog or frost under extreme conditions. As fogging and condensation frosting on a film involves molecular interaction with water prior to forming discrete droplets on the surface, it is essential to control the extent of a film to strongly bind with water molecules for antifogging coatings. While the water contact angle measurement is commonly used to probe the hydrophilicity of a film, it oftentimes fails to predict the antifogging and antifrosting performance as this value only reflects the wettability of a given surface to water droplet. In this work, a polysaccharide-based film composed of chitosan (CHI) and carboxymethyl cellulose (CMC) is used as the model system and oligo(ethylene glycol) (OEG) moieties are additionally introduced to study the effect of OEG moieties on antifogging and condensation frosting. We show that the film containing OEG-grafted CHI exhibits excellent frost-resistant capability due to the OEG moieties in the film that serve as active sites for water molecules to strongly interact in a nonfreezable state.

The development of stable and efficient electrocatalysts is of key importance for the establishment of a sustainable society. The activity of a metal electrocatalyst is determined by its electrochemically active surface area and intrinsic activity, which can be increased using highly porous structures and heteroatomic doping, respectively. Herein, we propose a general strategy of generating mesopores and residual oxygen in metal electrocatalysts by reduction of metastable metal oxides using Ag2O3 electrodeposited onto carbon paper as a model system and demonstrating that the obtained multipurpose porous Ag electrocatalyst has high activity for the electroreduction of O2 and CO2. The presence of mesopores and residual oxygen is confirmed by electrochemical and spectroscopic techniques, and quantum mechanical simulations prove the importance of residual oxygen for electrocatalytic activity enhancement. Thus, the adopted strategy is concluded to allow the synthesis of highly active metal catalysts with controlled mesoporosity and residual oxygen content.

The electronic structure of an atomic-layer-deposited MoS2 monolayer on SiO2 was investigated using X-ray absorption spectroscopy (XAS) and synchrotron X-ray photoelectron spectroscopy (XPS). The angle-dependent evolution of the XAS spectra and the photon-energy-dependent evolution of the XPS spectra were analyzed in detail using an ab-initio electronic structure simulation. Although similar to the theoretical spectra of an ideal free-standing MoS2 ML, the experimental spectra exhibit features that are distinct from those of an ideal ML, which can be interpreted as a consequence of S-O van der Waals (vdW) interactions. The strong consensus among the experimental and theoretical spectra suggests that the vdW interactions between MoS2 and adjacent SiO2 layers can influence the electronic structure of the system, manifesting a substantial electronic interaction at the MoS2-SiO2 interface.

We thank UNIST Central Research Facilities (UCRF) and Y. K. Kim for the cross-sectional high-resolution TEM images. This work was supported by Samsung Electronics (Samsung-SKKU Graphene/2D Center), the research fund (NRF-2017R1E1A1A01074493 and NRF-2019R1A4A1027934), the IBS (IBS-R-019-D1) and a grant (CASE-2013M3A6A5073173) from the Centre for Advanced Soft Electronics under the Global Frontier Research Program via the National Research Foundation of the Ministry of Science and ICT, South Korea. The NEXAFS experiments performed at the 4D, 6D and 10A2 beamlines of the Pohang Accelerator Laboratory (PAL) were supported in part by the Ministry of Science and ICT, POSTECH and UNIST. M.C. acknowledges support from Leverhulme Trust Research Grant RPG-2019-227. S.R., A.A. and M.C. acknowledge the European Union Horizon 2020 research and innovation programme for grant number 785219 and 881603 (Graphene Flagship). A.A. is supported by Project MECHANIC (PCI2018-093120) funded by Ministerio de Ciencia, Innovación y Universidades. The Catalan Institute of Nanoscience and Nanotechnology is funded by the CERCA Programme/Generalitat de Catalunya and supported by the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (grant number SEV-2017-0706).

In situ exsolution of metal nanoparticles (NPs) is emerging as an alternative technique to deliver thermally stable and evenly dispersed metal NPs, which exhibit excellent adhesion with conducting ...

Carbon hydrogasification is the slowest reaction among all carbon-involved small-molecule transformations. Here, we demonstrate a mechanochemical method that results in both a faster reaction rate and a new synthesis route. The reaction rate was dramatically enhanced by up to 4 orders of magnitude compared to the traditional thermal method. Simultaneously, the reaction exhibited very high selectivity (99.8 % CH

Understanding metal-to-insulator phase transitions in solids has been a keystone not only for discovering novel physical phenomena in condensed matter physics but also for achieving scientific breakthroughs in materials science. In this work, we demonstrate that the transport properties (i.e., resistivity and transition temperature) in the metal-to-insulator transitions of perovskite nickelates are tunable via the epitaxial heterojunctions of LaNiO3 and NdNiO3 thin films. A mismatch in the oxygen coordination environment and interfacial octahedral coupling at the oxide heterointerface allows us to realize an exotic phase that is unattainable in the parent compound. With oxygen vacancy formation for strain accommodation, the topmost LaNiO3 layer in LaNiO3/NdNiO3 bilayer thin films is structurally engineered and it electrically undergoes a metal-to-insulator transition that does not appear in metallic LaNiO3. Modification of the NdNiO3 template layer thickness provides an additional knob for tailoring the tilting angles of corner-connected NiO6 octahedra and the linked transport characteristics further. Our approaches can be harnessed to tune physical properties in complex oxides and to realize exotic physical phenomena through oxide thin-film heterostructuring.

Transition metal dichalcogenides (TMDs) are promising candidates for the semiconductor industry owing to their superior electrical properties. Their surface oxidation is of interest because their electrical properties can be easily modulated by an oxidized layer on top of them. Here, we demonstrate the XeF

Although anionic-redox-based layered oxide materials have attracted great attention as promising cathodes for Na-ion batteries because of their high practical capacities, they suffer from undesirable structural degradation, resulting in the poor electrochemical behavior. Moreover, the occurrence of stable anionic-redox reaction without the use of expensive elements such as Li, Co, and Ni is considered one of the most important issues for high-energy and low-cost Na-ion batteries. Herein, using first-principles calculation and various experimental techniques, we investigate the combination of vacancy (□) and Ti4+ cations in the transition-metal sites to enable outstanding anionic-redox-based electrochemical performance in the Na-ion battery system. The presence of vacancies in the P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 structure suppresses the large structural change such as the P2–OP4 phase transition, and Ti4+ cations in the structure result in selectively oxidized oxygen ions with structural stabilization during Na+ deintercalation in the high-voltage region. The high structural stability of P2-type Na0.56[Ti0.1Mn0.76□0.14]O2 enables not only the high specific capacity of 224.92 mAh g−1 at 13 mA g−1 (1C = 264.1 mA g−1) with an average potential of ∼2.62 V (vs Na+/Na) but also excellent cycle performance with a capacity retention of ∼80.38% after 200 cycles at 52 mA g−1 with high coulombic efficiencies above 99%. Although there are some issues such as low Na contents in the as-prepared state, these findings suggest potential strategies to stabilize the anionic-redox reaction and structure in layered-oxide cathodes for high-energy and low-cost Na-ion batteries.

van der Waals (vdW) materials have shown unique electrical and optical properties depending on the thickness due to strong interlayer interaction and symmetry breaking at the monolayer level. In co...

Polymer dielectric materials with hydroxyl functionalities such as poly(4-vinylphenol) and poly(vinyl alcohol) have been utilized widely in organic thin-film transistors (OTFTs) because of their ex...

The introduction of ferromagnetic order in topological insulators in general breaks the time-reversal symmetry and a gap is opened in topological surface bands. Various studies have focused on gap-opened magnetic topological insulators, because such modified band structures provide a promising platform for observing exotic quantum physics. However, the role of antiferromagnetic order in topological insulators is still controversial. In this report, we demonstrate that it is possible to restore the topological surface states by effectively reducing the antiferromagnetic ordering in Gd-substituted Bi2Te3. We successfully control the magnetic impurities via thermal treatments in ultra-high vacuum condition and observe apparent restoration of topological surface band dispersions. The microscopic mechanism of atomic rearrangements and the restoration process of topological surface states are unraveled by the combination of scanning tunneling microscopy measurements and density functional theory calculations. This work provides an effective way to control the magnetic impurities which is strongly correlated with topological surface states.

The electronic structure of an atomic-layer-deposited MoS

Soluble aromatic polyimides and polyvinyls were prepared by incorporating pyridine moiety and its derivatives in the backbone and the side groups, respectively: 6F-Py-i polymers based on the polyimide backbone (6F-Py-1 to 6F-Py-7) and PVPy-i polymers based on the polyvinyl backbone (PVPy-1 to PVPy-4). All polymers were found to be amorphous. The 6F-Py-i polymers were thermally stable up to 511–545 °C; the PVPy-i polymers were stable up to 362–376 °C. Their glass transitions, thin film densities, molecular orbitals, and band gaps were determined. The electrical devices fabricated with the polymers in an electrode/polymer/electrode structure revealed p-type unipolar write-once-read-many times (namely, permanent) or dynamic random access memory or dielectric behavior, depending on the substituents of the pyridine unit and the film thicknesses. In particular, such digital memory characteristics were found to originate from the pyridine moieties possessing a high charge affinity in the polymers. However, the pyridine moieties were found to still need at least two or more aromatic substituents to get enough power to stabilize charges via utilizing the resonance effects provided by the substituents. Overall, this study demonstrated that the pyridine unit conjugated with two or more aromatic substituents is a very useful component to design and synthesize digital memory materials based on thermally stable polyimides and other high performance polymers. The 6F-Py-i polymers have potential for the low-cost mass production of high-performance programmable unipolar permanent memory devices with very low power consumption.

With increasing demand for transparent conducting electrodes, graphene has attracted considerable attention, owing to its high electrical conductivity, high transmittance, low reflectance, flexibility, and tunable work function. Two faces of single-layer graphene are indistinguishable in its nature, and this idea has not been doubted even in multilayered graphene (MLG) because it is difficult to separately characterize the front (first-born) and the rear face (last-born) of MLG by using conventional analysis tools, such as Raman and ultraviolet spectroscopy, scanning probe microscopy, and sheet resistance. In this paper, we report the striking difference of the emission pattern and performance of transparent organic light-emitting diodes (OLEDs) depending on the adopted face of MLG and show the resolved chemical and physical states of both faces by using depth-selected absorption spectroscopy. Our results strongly support that the interface property between two different materials rules over the bulk property in the driving performance of OLEDs.

In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI3 perovskite film changes to an intermediate phase and decomposes to CH3I, NH3, and PbI2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH3NH3+ organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. However, the FeO2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.

Hydrogen spillover is a catalytic process that occurs by surface reaction and subsequent diffusion to reversibly provide a massive amount of hydrogen dopants in correlated oxides, but the mechanism at the surface of correlated oxides with metal catalyst are not well understood. Here we show that a significant amount of oxygen is released from the surface of correlated VO2 films during hydrogen spillover, contrary to the well-established observation of the formation of hydrogen interstitials in the bulk part of VO2 films. By using ambient-pressure X-ray photoelectron spectroscopy, we prove that the formation of surface oxygen vacancies is a consequence of a favorable reaction for the generation of weakly adsorbed H2O from surface O atoms that have low coordination and weak binding strength. Our results reveal the importance of in situ characterization to prove the dynamic change during redox reaction and present an opportunity to control intrinsic defects at the surface.

Polymer dielectric materials with hydroxyl functionalities such as poly(4-vinylphenol) and poly(vinyl alcohol) have been utilized widely in organic thin-film transistors (OTFTs) because of their excellent insulating performance gained by hydroxyl-mediated cross-linking. However, the polar hydroxyl functionality also deleteriously affects the performance of OTFTs and significantly impairs the device stability. In this study, a sub-20 nm, high

Sporadic catalytic decomposition because of the presence of Au grains is a significant issue to be clarified in electronic devices. Here, we report the inhomogeneous dissociation of native silicon oxide depending on the electronic structure of Au grains using scanning photoelectron microscopy. Upon annealing, the oxygen atoms dissociated from native SiOx layer out-diffuses in non-uniform manner, resulting in oxidize the Au layer. Valence band spectra showed that the spit-orbit splitting, directly related to the coordination number, differs from site to site. Scanning photoelectron microscopy images show that dissociated SiOx coincides with the regions where low-coordinated Au resides. These results imply that Au with low coordination number activated the dissociation of SiOx and open new pathway to remove undesirable oxide layer at relatively low temperature. Copyright © 2016 John Wiley & Sons, Ltd.

We firstly report an experimental visualization of a cycloaddition reaction on RT frozen asymmetric Si dimers. The frozen Si dimers with a local c(4 × 2) order were prepared by pinning flip-flopping Si dimers by using molecules. This RT pristine c(4 × 2) structure was used to determine what Si atom of an asymmetric Si dimer bonds to a molecule at the initial stage of the RT cycloaddition reaction, which has been a long-standing puzzling issue. This made it possible to compare directly experimental cycloaddition reactions with theoretical ones. As a prototype for the experiment, a 1,3-butadiene molecule adsorbed between Si dimer rows was used. The 1,3-butadiene molecule was found to prefer a symmetric Si pair on the frozen Si dimers, i.e., two electrophilic lower atoms of asymmetric Si dimers. This result is consistent with the theoretical prediction that a 1,3-diene molecule prefers a symmetric Si pair on the Si(001)c(4 × 2) surface. This experimental approach can also be applied to other studies for the adsorption of a molecule on a Si(001) surface at room temperature.

We present a new method for transferring chemical vapor deposition (CVD)-grown graphene onto the surfaces of organic materials directly. Raman and near edge X-ray absorption fine structure measurements prove that high-quality and single layer graphene/organic thin films can be obtained with minimized impurity introduction. In-situ synchrotron radiation photoemission spectroscopy combined with ultraviolet photoelectron spectroscopy experiments demonstrate that the inserted graphene can not only act as a buffer layer to reduce the interfacial chemical reactions between the deposited Al and organic materials, but also tune the metal/organic interface electronic structure significantly. This new graphene transfer technique may have a great potential in the application of engineering the metal–organic interface properties, which is one of the key technologies for the optimal design and fabrication of organic electronic and optoelectronic devices.

We investigated the surface property change of indium tin oxide (ITO) with the various cleaning methods, using photoemission spectroscopy (PES), work function change and near-edge X-ray adsorption ne structure (NEXAFS). The detergent treatments of ITO with acetone (C3H6O), methanol (CH4O), 2-propanol (C3H8O), and deionized (D) water yielded work function shifts as high as 0.99 eV compared to the no-treatment ITO. In contrast, work function shifts of 0.10 0.35 eV were measured after other treatments. The lowest C 1s concentration was obtained after O2 plasma treatment of ITO. There was no big change in the peak position and the shape of In 3d, and Sn 3d2 after each treatment. But C 1s and O 1s spectra shows a peak shift and shape change. Presence of carbon can be minimized by NaOH treatment combined with oxygen plasma. In NEXAFS spectra of C K-edge on each sample, we found two π-binding states whose positions are 284.5 and 287.9 eV, C=C and C=O, respectively.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO

We report spatially-resolved spectroscopic investigations on the effect of annealing a Pt (100 A)/Si interface in the presence of a native silicon oxide layer. Scanning photoelectron microscopy showed a spatially non-uniform growth pattern of PtSi depending on the annealing temperature and annealing time. Pt 4 f and Si 2 p core-level spectra measured using different photon energies and at different points suggest both in-plane and out-of-plane inhomogeneous growth of PtSi at 773 K.

We report catalytic decomposition of few-layer graphene on an Au/SiOx/Si surface wherein oxygen is supplied by dissociation of the native SiOx layer at a relatively low temperature of 400 °C. The detailed chemical evolution of the graphene covered SiOx/Si surface with and without gold during the catalytic process is investigated using a spatially resolved photoelectron emission method. The oxygen atoms from the native SiOx layer activate the gold-mediated catalytic decomposition of the entire graphene layer, resulting in the formation of direct contact between the Au and the Si substrate. The notably low contact resistivity found in this system suggests that the catalytic depletion of a SiOx layer could realize a new way to micromanufacture high-quality electrical contact.

Graphene has shown great application opportunities in future nanoelectronic devices because of its outstanding electronic properties. Moreover, its impressive optical properties have been attracting the interest of researchers, and, recently, the photovoltaic effects of a heterojunction structure embedded with few layer graphene (FLG) have been demonstrated. Here, we report the photovoltaic response of graphene–semiconductor junctions and the controlled open-circuit voltage (Voc) with varying numbers of graphene layers. After unavoidably adsorbed contaminants were removed from the FLGs by means of in situ annealing, prepared by layer-by-layer transfer of the chemically grown graphene layer, the work functions of FLGs showed a sequential increase as the graphene layers increase, despite random interlayer-stacking, resulting in the modulation of photovoltaic behaviors of FLGs/Si interfaces. The surface photovoltaic effects observed here show an electronic realignment in the depth direction in the FLG heterojunction systems, indicating future potential toward solar devices utilizing the excellent transparency and flexibility of FLG. Copyright © 2011 John Wiley & Sons, Ltd.