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Preparation of edge-rich two-dimensional (2D) transition metal dichalocogenides (TMDs) has been actively investigated with the aim to improve their electrical and catalytic properties. Here, we elucidate the role of potassium ions in oxidation of TMDs and suggest a consequent novel anisotropic etching mechanism driven by self-running oxide droplets. We discover that potassium-mediated oxidation of MoS2 leads to the formation of K-intercalated hexagonal-phase molybdenum oxides (h-KxMoO3), whereas orthorhombic-phase oxides are formed in the absence of potassium ions. Metastable h-KxMoO3 appears to have decomposed into oxide droplets at higher temperature. Self-running of the oxide droplets leads to layer-by-layer anisotropic etching of MoS2 along the armchair direction. The motion of the droplets appears to be triggered by the surface energy instability between the oxide droplets and the underlying MoS2 layer. This study opens new possibilities to design and manufacture novel edge-rich 2D TMDs that do not follow the equilibrium Wulff shape by modulating their oxidation with the assistance of alkali metals and also offers fundamental insights into the interactions between nanodroplets and 2D materials toward edge engineering.

Although solid-state phase transformations through chemical reaction with the surrounding environment are important in the field of materials science, the atomic-level dynamics at reacting surfaces have been difficult to observe directly. Herein, we found highly ordered arrays of 1D intermediate crystals with a unique atomic configuration during the thermal sulfidation of 3D-structured MoO2 to 2D layer-structured MoS2. These arrays reveal a dimension-breaking reconstruction process (3D → 1D → 2D) as well as a unique electronic structure evolution. Theoretical calculations show that the 1D crystals have a cross-sectional structure of four transition-metal atoms arranged in a diamond shape; these are critical to the atomic layer-by-layer formation of 2D transition-metal dichalcogenides. Furthermore, electronic structure analyses reveal that the 1D intermediate crystals alter the MoO2/MoS2 contact structure from p- to n-type with increases in the number of formed MoS2 layers.

The electronic, catalytic, and optical properties of transition metal dichalcogenides (TMDs) are significantly affected by oxidation, and using oxidation to tune the properties of TMDs has been actively explored. In particular, because transition metal oxides (TMOs) are promising hole injection layers, a TMD-TMO heterostructure can be potentially applied as a p-type semiconductor. However, the oxidation of TMDs has not been clearly elucidated because of the structural instability and the extremely small quantity of oxides formed. Here, we reveal the phases and morphologies of oxides formed on two-dimensional molybdenum disulfide (MoS2) using transmission electron microscopy analysis. We find that MoS2 starts to oxidize around 400 °C to form orthorhombic-phase molybdenum trioxide (α-MoO3) nanosheets. The α-MoO3 nanosheets so formed are stacked layer-by-layer on the underlying MoS2 via van der Waals interaction and the nanosheets are aligned epitaxially with six possible orientations. Furthermore, the band gap of MoS2 is increased from 1.27 to 3.0 eV through oxidation. Our study can be extended to most TMDs to form TMO-TMD heterostructures, which are potentially interesting as p-type transistors, gas sensors, or photocatalysts.

A key challenge in the development of two-dimensional (2D) devices is the fabrication of metal–semiconductor junctions with minimal contact resistance and depinned energy levels. An ideal solution for practical applications is to make contacts between 2D van der Waals semiconductors and 2D van der Waals metals. Here we report the wafer-scale production of patterned layers of metallic transition metal ditellurides on different substrates. Our tungsten ditelluride and molybdenum ditelluride layers, which are grown using a tellurization process applied to a precursor transition metal layer, have an electronic performance comparable to that of mechanically exfoliated flakes and can be combined with the 2D semiconductor molybdenum disulfide. The resulting metal–semiconductor junctions are free from significant disorder effects and Fermi-level pinning, and are used to create monolayer molybdenum disulfide field-effect transistors. The Schottky barrier heights of the devices also largely follow the trend of the Schottky–Mott limit. Two-dimensional metallic WTe2 and MoTe2 layers can be combined with a semiconducting MoS2 monolayer to create metal–semiconductor junctions that are free from substantial disorder effects and Fermi-level pinning.

HfO2-based ferroelectrics are highly expected to lead the new paradigm of nanoelectronic devices owing to their unexpected ability to enhance ferroelectricity in the ultimate thickness scaling limit (≤2 nm). However, an understanding of its physical origin remains uncertain because its direct microstructural and chemical characterization in such a thickness regime is extremely challenging. Herein, we solve the mystery for the continuous retention of high ferroelectricity in an ultrathin hafnium zirconium oxide (HZO) film (∼2 nm) by unveiling the evolution of microstructures and crystallographic orientations using a combination of state-of-the-art structural analysis techniques beyond analytical limits and theoretical approaches. We demonstrate that the enhancement of ferroelectricity in ultrathin HZO films originates from textured grains with a preferred orientation along an unusual out-of-plane direction of (112). In principle, (112)-oriented grains can exhibit 62% greater net polarization than the randomly oriented grains observed in thicker samples (>4 nm). Our first-principles calculations prove that the hydroxyl adsorption during the deposition process can significantly reduce the surface energy of (112)-oriented films, thereby stabilizing the high-index facet of (112). This work provides new insights into the ultimate scaling of HfO2-based ferroelectrics, which may facilitate the design of future extremely small-scale logic and memory devices.

Among the different growth mechanisms for two-dimensional (2D) hexagonal boron nitride (h-BN) synthesized using chemical vapor deposition, spiraling growth of h-BN has not been reported. Here we report the formation of intertwined double-spiral few-layer h-BN that is driven by screw dislocations located at the antiphase boundaries of monolayer domains. The microstructure and stacking configurations were studied using a combination of dark-field and atomic resolution transmission electron microscopy. Distinct from other 2D materials with single-spiral structures, the double-spiral structure enables the intertwined h-BN layers to preserve the most stable AA′ stacking configuration. We also found that the occurrence of shear strains at the boundaries of merged spiral islands is dependent on the propagation directions of encountering screw dislocations and presented the strained features by density functional theory calculations and atomic image simulations. This study unveils the double-spiral growth of 2D h-BN multilayers and the creation of a shear strain band at the coalescence boundary of two h-BN spiral clusters. National Research Foundation (NRF) Accepted version This work was supported by IBS-R019-D1, the National Research Foundation (NRF) grant funded by the Korea government (MSIT) (2018R1A2A2A05019598), and the NRF-ANR Joint (NRF2016-NRF-ANR001).

A graphene-based porous electrode for a lithium–oxygen (Li–O2) battery is investigated for use in next generation energy storage systems. The porosity of the cathode electrode in Li–O2 batteries is a key factor in increasing their oxygen diffusion rate and electrochemical activity, and enables a longer cycle life. In addition, the adsorption behavior of the electrolyte is an important factor for the charging process and diffusion of oxygen. We report the fabrication of a restacking-inhibited film cathode using corrugated and highly porous reduced graphene flakes that have an outstanding capacity and cycle life. We have demonstrated a robust porous cathode film for the next generation Li–O2 batteries, which provides (1) rich voids and spaces for oxygen-related reactions, (2) easy accessibility to the electrolyte and rapid oxygen diffusion. This study can be applied for the design of new solution-processed graphene and the development of Li–O2 battery cathodes.

The objective of this study was to determine detailed microstructure of a Ni1–xPtxSi film formed via a melting/quenching process using high temperature laser annealing on a Si(001) substrate. The orthorhombic Ni1–xPtxSi film was found to be able to epitaxially grow with a crystallographic relationship of Ni1–xPtxSi[010]//Si[110], Ni1–xPtxSi(400)//Si(3 3 ¯ 1), and Ni1–xPtxSi (104)//Si(004). Volume expansion of the Ni1–xPtxSi film due to Pt incorporation was mainly accommodated by an increase in only one direction nearly parallel to the film surface (lattice parameter a). This was explained by the minimum coherent strain at the Ni1–xPtxSi (104)/Si(004) interface with an epitaxial growth tendency. Atomic-scale scanning transmission electron microscopy analyses revealed that the interface of Ni1–xPtxSi/Si had a repetitive atomic-step feature with energetically favorable Ni1–xPtxSi(004) terraces and (400) structural ledges that could increase the coherent area. By generating an array of misfit dislocations with an extra half plane of Ni1–xPtxSi(020), the elastic strain was further relieved.

Wafer-scale growth of transition metal dichalcogenides with precise control over the number of layers, and hence the electronic state is an essential technology for expanding the practical application of 2D materials. Herein, a new growth method, phase-transition-induced growth (PTG), is proposed for the precisely controlled growth of molybdenum disulfide (MoS2 ) films consisting of one to eleven layers with spatial uniformity on a 2 in. wafer. In this method, an energetically unstable amorphous MoSx Oy (a-MoSx Oy ) phase is effectively converted to a thermodynamically stable crystalline MoS2 film. The number of MoS2 layers is readily controlled layer-by-layer by controlling the amount of Mo atoms in a-MoSx Oy , which is also applicable for the growth of heteroatom-inserted MoS2 . The electronic states of intrinsic and Nb-inserted MoS2 with one and four layers grown by PTGare are analyzed based on their work functions. The work function of monolayer MoS2 effectively increases with the substitution of Nb for Mo. As the number of layers increases to four, charge screening becomes weaker, dopant ionization becomes easier, and ultimately the work function increases further. Thus, better electronic state modulation is achieved in a thicker layer, and in this respect, PTG has the advantage of enabling precise control over the film thickness.

Graphene-based two-dimensional heterostructures are of substantial interest both for fundamental studies and their various potential applications. Particularly interesting are atomically thin semiconducting oxides on graphene, which uniquely combine a wide band gap and optical transparency. Here, we report the atomic-scale investigation of a novel self-formation of a ZnO monolayer from the Zn metal on a graphene oxide substrate. The spontaneous oxidation of the ultrathin Zn metal occurs by a reaction with oxygen supplied from the graphene oxide substrate, and graphene oxide is deoxygenated by a transfer of oxygen from O-containing functional groups to the zinc metal. The ZnO monolayer formed by this spontaneous redox reaction shows a graphene-like structure and a band gap of about 4 eV. This study demonstrates a unique and straightforward synthetic route to atomically thin two-dimensional heterostructures made from a two-dimensional metal oxide and graphene, formed by the spontaneous redox reaction of a very thin metal layer directly deposited on graphene oxide.

Point defects in freestanding graphene monolayers such as monovacancies (MVs) and divacancies have been investigated at atomic scale with aberration-corrected transmission electron microscopy and theoretical calculations. In general, these defects can be formed simply by the absence of individual carbon atoms and carbon bond reconstructions in the graphene lattice under electron and ion irradiation. However, in this study, we found that oxygen and hydrogen atoms can be involved in the formation of these point defects caused by the simultaneous detachment of oxygen–carbon atoms. Here we report the effect of the oxygen and hydrogen atoms on the graphene surface forming the point defects under electron beam irradiation, and their role of stabilizing other MVs when composed of 13–5 ring pairs. In addition, theoretical analysis using density functional theory calculations demonstrates that the participating atoms can form the point defects in the intermediate states and stabilize 13–5 ring pairs under electron beam irradiation.

Atomically thin binary 2-dimensional (2D) semiconductors exhibit diverse physical properties depending on their composition, structure and thickness. By adding another element in those materials, which will lead to formation of ternary 2D materials, the property and structure would greatly change and significantly expanded applications could be explored. In this work, we report structural and optical properties of atomically thin chromium thiophosphate (CrPS4), a ternary antiferromagnetic semiconductor. Its structural details were revealed by X-ray and electron diffractions. Transmission electron microscopy showed that preferentially-cleaved edges are parallel to diagonal Cr atom rows, which readily identified their crystallographic orientations. Strong in-plane optical anisotropy induced birefringence that also enabled efficient determination of crystallographic orientation using polarized microscopy. The lattice vibrations were probed by Raman spectroscopy for the first time and exhibited significant dependence on thickness of crystals exfoliated down to single layer. Optical absorption determined by reflectance contrast was dominated by d-d type transitions localized at Cr3+ ions, which was also responsible for the major photoluminescence peak at 1.31 eV. The spectral features in the absorption and emission spectra exhibited noticeable thickness-dependence and hinted a high photochemical activity for single layer CrPS4. The current structural and optical investigation will provide a firm basis for future study and application of this novel magnetic semiconductor., Comment: 32 pages, 5 figures

Antiphase boundaries (APBs) in 2D transition metal dichalcogenides have attracted wide interest as 1D metallic wires embedded in a semiconducting matrix, which could be exploited in fully 2D‐integrated circuits. Here, the anisotropic morphologies of APBs (i.e., linear and saw‐toothed APBs) in the nanoscale are investigated. The experimental and computational results show that despite their anisotropic nanoscale morphologies, all APBs adopt a predominantly chalcogen‐oriented dense structure to maintain the energetically most stable atomic configuration. Moreover, the effect of the nanoscale morphology of an APB on electron transport from two‐probe field effect transistor measurements is investigated. A saw‐toothed APB has a considerably lower electron mobility than a linear APB, indicating that kinks between facets are the main factors of scattering. The observations contribute to the systematical understanding of the faceted APBs and its impact on electrical transport behavior and it could potentially extend the applications of 2D materials through defect engineering to achieve the desired properties., Herein, the anisotropic nanoscale features of antiphase boundaries in 2H phase of transition metal dichalcogenides are investigated (i.e., saw‐toothed for transition metal‐facing and linear for chalcogen‐facing antiphase boundaries) in order to preserve the thermodynamically most stable atomic configurations. In addition, they have different in‐plane transport behavior because lots of kinks in the saw‐toothed antiphase boundary act as scattering centers.

Gallium selenide (GaSe) is one of layered group-III metal monochalcogenides, which has an indirect bandgap in monolayer and direct bandgap in bulk unlike other conventional transition metal dichalcogenides (TMDs) such as MoX2 and WX2 (X=S and Se). Four polytypes of bulk GaSe, designated as beta-, epsilon-, gamma-, and delta-GaSe, have been reported. Since different polytypes result in different optical and electrical properties even for the same thickness, identifying the polytype is essential in utilizing this material for various optoelectronic applications. We performed polarized Raman measurement on GaSe and found different ultra-low-frequency Raman spectra of inter-layer vibrational modes even for the same thickness due to different stacking sequences of the polytypes. By comparing the ultra-low-frequency Raman spectra with theoretical calculations and high-resolution electron microscopy measurements, we established the correlation between the ultra-low-frequency Raman spectra and the stacking sequences for trilayer GaSe. We further found that the AB-type stacking is more stable than the AA'-type stacking in GaSe.

Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) have attracted considerable attention as promising building blocks for a new generation of gas-sensing devices because of their excellent electrical properties, superior response, flexibility, and low-power consumption. Owing to their large surface-to-volume ratio, various 2D TMDCs, such as MoS2, MoSe2, WS2, and WSe2, have exhibited excellent gas-sensing characteristics. However, exploration toward the enhancement of TMDC gas-sensing performance has not yet been intensively addressed. Here, we synthesized large-area uniform WS2 xSe2-2 x alloys for room-temperature gas sensors. As-synthesized WS2 xSe2-2 x alloys exhibit an elaborative composition control owing to their thermodynamically stable sulfurization process. Further, utilizing uniform WS2 xSe2-2 x alloys over a large area, we demonstrated improved NO2-sensing performance compared to WSe2 on the basis of an electronic sensitization mechanism. The WS0.96Se1.04 alloy gas sensor exhibits 2.4 times enhanced response for NO2 exposure. Further, we demonstrated a low-power wearable NO2-detecting wristband that operates at room temperature. Our results show that the proposed method is a promising strategy to improve 2D TMDC gas sensors and has a potential for applications in advanced gas-sensing devices.

The structural, electrical, and optical properties of monolayer ruthenium oxide (RuO2) nanosheets (NSs) fabricated by chemical exfoliation of a layered three-dimensional form of K-intercalated RuO2 are studied systematically via experimental and computational methods. Monolayer RuO2 NS is identified as having a distorted h-MX2 structure. This is the first observation of a RuO2 NS structure that is unlike the t-MX2 structure of the RuO2 layers in the parent material and does not have hexagonal symmetry. The distorted h-MX2 RuO2 NSs are shown to have optical transparency superior to that of graphene, thereby predicting the feasibility of applying RuO2 NSs to flexible transparent electrodes. In addition, it is demonstrated that the semiconducting band structures of RuO2 NSs can be manipulated to be semi-metallic by adjusting the crystal structure, which is related to band-gap engineering. This finding indicates that RuO2 NSs can be used in a variety of applications, such as flexible transparent electrodes, atomic-layer devices, and optoelectronic devices. Nanosheets of ruthenium oxide could make excellent transparent electrical contacts, show researchers from Korea. Graphene is the wonder material of the last decade owing to its amazing electrical, mechanical and thermal properties. Scientists are thus keen to fabricate single layers of atoms other than carbon. Now, Dong-Su Ko, Jung-Hwa Kim and Jong Wook Roh from the Samsung Advanced Institute of Technology and co-workers have combined experiments and theory to fully characterize this unusual two-dimensional material. They created their nanosheets by exfoliating a three-dimensional block of ruthenium oxide. Transmission electron microscopy, X-ray diffraction experiments and first-principles calculations showed that the two-dimensional material has a distorted atomic arrangement, which makes it a semiconductor rather than a metal like its parent material. Furthermore, ruthenium oxide nanosheets are more transparent than graphene, making them useful for flexible transparent electrodes. As a new two-dimensional (2D) material, monolayer ruthenium oxide (RuO2) nanosheets (NSs) have distorted h-MX2 type crystal structures that lead to semiconducting properties and good optical transmittance. This study suggests that monolayer RuO2 can be useful in applications of flexible optoelectronics.

Non-toxic InP-based nanocrystals have been developed for promising candidates for commercial optoelectronic applications and they still require further improvement on photophysical properties, compared to Cd-based quantum dots (QDs), for better device efficiency and long-term stability. It is, therefore, essential to understand the precise mechanism of carrier trapping even in the state-of-the-art InP-based QD with near-unity luminescence. Here, it is shown that using time-resolved spectroscopic measurements of systematically size-controlled InP/ZnSe/ZnS core/shell/shell QDs with the quantum yield close to one, carrier trapping decreases with increasing the energy difference between band-edge and trap states, indicating that the process follows the energy gap law, well known in molecular photochemistry for nonradiative internal conversion between two electronic states. Similar to the molecular view of the energy gap law, it is found that the energy gap between the band-edge and trap states is closely associated with ZnSe phonons that assist carrier trapping into defects in highly luminescent InP/ZnSe/ZnS QDs. These findings represent a striking departure from the generally accepted view of carrier trapping mechanism in QDs in the Marcus normal region, providing a step forward understanding how excitons in nanocrystals interact with traps, and offering valuable guidance for making highly efficient and stable InP-based QDs.

The initial neutral beam heating experiment in Versatile Experiment Spherical Torus (VEST) has been conducted via neutral beam characterizations such as neutralization efficiency, beam fraction, and shine-through loss. For the neutralization efficiency and shine-through loss estimation, a secondary electron emission (SEE) detector, which can be used in rapidly changing plasma, has been developed. The measurement results of the monatomic fraction by Doppler shift spectroscopy and the neutralization efficiency by SEE detector are 65%, and 70%, respectively. The shine-through loss measurement shows that the injection of a 12 keV neutral beam into a typical ohmic discharge of VEST results in a large amount of shine-through loss. To reduce the shine-through loss, a new target plasma discharge (0.17 T, 120 kA, 13 ms) with increased plasma density of ~ 2 × 10 19 m − 3 is developed by providing additional gas injection. The electron-heating effect has been successfully observed for this target plasma with a 200 kW neutral beam injection at the beam energy of 12 keV. The electron temperature increases from 20 to 68 eV without significant density change when the neutral beam is injected.

We report a new family of inorganic ligands, namely, transition metal-based thiometallates, for the surface functionalization of colloidal nanocrystals (NCs). We synthesized Pt-, Fe-, Co-, and Ni-based thiometallates, in which transition metal ions were complexed with polysulfides. These inorganic anions easily exchanged the surface organic ligands of various nanocrystals of metal, semiconductor, and oxide materials, without affecting the NCs’ primary structural and optical characteristics. Furthermore, upon heating, these complexes were decomposed and transformed into crystalline phases of metal sulfides or pure metals, accompanied by the evaporation of S. Based on this effect, we selectively synthesized homogeneously distributed atomic Pt clusters or Pt nanoparticles on Fe3O4 nanomaterials by heating thioplatinate-capped Fe3O4 NCs. As a model application, we tested the prepared Pt-functionalized Fe3O4 nanomaterial as a heterogeneous catalyst for CO oxidation reaction and Pt–Fe3O4 catalysts exhibited the...

The growing popularity of Li-ion batteries in the field of energy storage necessitates the constant development of methods for improving their performance. To address this task, this study describes the effect of transition metal (TM = Al, Co, Fe) phosphate coatings on the electrochemical performance of Li1.0Ni0.8Co0.15Mn0.05O2 positive electrode materials, highlighting the importance of the TM/P mole ratio, and reveals that decreased amounts of Li residuals were observed for all coated samples. Considering Li residual removal as well as capacity and capacity retention upon cycling, the most effective surface modification was achieved in the case of a 1:1 Co/P coating, which increased initial capacity and capacity retention by 10 mAh g−1 and 3%, respectively, as compared to the uncoated sample. Moreover, the beneficial effect of the above Co/P coating is also confirmed for the more Ni-rich Li1.0Ni0.91Co0.06Mn0.03O2.

Spinel-embedded lithium-rich oxides are synthesized and their structural phases are analyzed. The type of spinel LiM0.5Mn1.5O4 (M = Ni, Co, Mn) embedded is varied by controlling the spinel composition and content. Of the various composites fabricated with different spinel phases, the LiCo0.5Mn1.5O4-embedded over-lithiated layered oxide (OLO) shows the best electrochemical performance as a cathode because of the absence of a parasitic phase and its high structural stability. The formation energy of the LiCo0.5Mn1.5O4-embedded oxide is determined through first-principles calculations and is found to be lower than that of the pristine oxide as well as other spinel-phase-embedded oxides. It is also observed that use of OLO with optimal embedded spinel LiCo0.5Mn1.5O4 in a cylindrical 18650-type cell results in improvement in the full-cell electrochemical performance.

Transition to a commensurate state changes the local symmetry periodicity on two-dimensional van der Waals superstructures, evoking distinctive properties far beyond individual layers. We investigate the morphology of moiré superstructures of graphene on hexagonal boron nitride (hBN) with a low twist angle (≈0°) through moiré fringe analyses with dark field transmission electron microscopy. The moiré fringes exhibit local variation, suggesting that the interaction between graphene and hBN depends on the stacking configuration and that local transition to the commensurate state occurs through the reduced crystalline mismatch (that is, by lattice stretching and twisting on the graphene lattices). This moiré superstructure analysis suggests an inventive method for studying the interaction between stacked van der Waals layers and for discerning the altered electronic and optical properties of graphene on hBN superstructures with a low twist angle, even at low magnification.

A hybrid gate dielectric material for flexible OTFT is developed by using core–shell nanoparticles (SiO2@PSRXL) where the core and the shell consist of silica nanoparticles and polysiloxane resin, respectively. Since polysiloxane resin contains both thermal- and photo-crosslinkable functional groups, densely-crosslinked thin gate dielectric films can be easily prepared on various substrates by conventional solution casting followed by dual crosslinking. SiO2@PSRXL films exhibit high thermal stability (weight loss at 300 °C is smaller than 3 wt%). The dielectric films made of SiO2@PSRXL show an exceptionally low leakage current and no breakdown voltage up to 4.3 MV cm−1, which are comparable to those of silica dielectrics prepared by CVD. OTFT devices based on dibenzothiopheno[6,5-b:6′,5′-f]thieno[3,2-b]thiophene (DTBTT) as a semiconductor and SiO2@PSRXL as a gate dielectric exhibit good hole mobility (2.5 cm2 V−1 s−1) and Ion/Ioff ratio (106).

In this work, organic photodiodes (OPDs) based on two newly synthesized p-type dipolar small molecules are reported for application to green-light-selective OPDs. In order to reduce the blue-color absorption induced by the use of C60 as the n-type material in a bulk heterojunction (BHJ), the electron donor:electron acceptor composition ratio is tuned in the BHJ. With this light manipulation approach, the blue-wavelength external quantum efficiency (EQE) is minimized to 18% after reducing the C60 concentration in the center part of the BHJ. The two p-type molecules get a cyanine-like character with intense and sharp absorption in the green color by adjusting the strength of their donating and accepting parts and by choosing a selenophene unit as a π-linker. When combined to C60, the green-wavelength EQE reaches 70% in a complete device composed of two transparent electrodes. Finally, the optical simulation shows the good color-balance performance of hybrid full-color image sensor without an additional filter by using the developed green OPD as the top-layer in stacked device architecture.

Graphene, which is one of the most promising materials for its state-of-the-art applications, has received extensive attention because of its superior mechanical properties. However, there is little experimental evidence related to the mechanical properties of graphene at the atomic level because of the challenges associated with transferring atomically-thin two-dimensional (2D) materials onto microelectromechanical systems (MEMS) devices. In this study, we show successful dry transfer with a gel material of a stable, clean, and free-standing exfoliated graphene film onto a push-to-pull (PTP) device, which is a MEMS device used for uniaxial tensile testing in in situ transmission electron microscopy (TEM). Through the results of optical microscopy, Raman spectroscopy, and TEM, we demonstrate high quality exfoliated graphene on the PTP device. Finally, the stress–strain results corresponding to propagating cracks in folded graphene were simultaneously obtained during the tensile tests in TEM. The zigzag and armchair edges of graphene confirmed that the fracture occurred in association with the hexagonal lattice structure of graphene while the tensile testing. In the wake of the results, we envision the dedicated preparation and in situ TEM tensile experiments advance the understanding of the relationship between the mechanical properties and structural characteristics of 2D materials. Electronic supplementary material The online version of this article (10.1007/s42649-019-0005-5) contains supplementary material, which is available to authorized users.

A Thomson scattering (TS) system has been utilized to measure the electron temperature and density of the core region of Versatile Experiment Spherical Torus (VEST). Recently, the laser injection system is successfully upgraded adopting the burst laser with the repetition rate of 1 kHz and the energy of 2 J. Furthermore, improved collection optics with additional polychromators and a 32-channel fast digitizer are prepared to observe the fast time evolution of radial profiles. This improvement is essential to study fast phenomena such as internal reconnection event (IRE). We increase the TS signal and reduce the stray light by introducing new filters having better optical properties such as high optical density at 1064 nm, transmission, and reflectance. Moreover, the optimum reverse bias voltages are newly set to make the system operational independent of the background radiation. As a result, 1 kHz radial profiles of the core electron temperature and density are measured for the first time, showing characteristics of IREs in VEST.

Solid electrolytes (SE) are key components for the safe and continuous operation of high-energy lithium metal batteries. Metal oxide SEs, which are stable under ambient conditions, are used as separators in the form of thick and heavy plates; however, this reduces the specific energy of practical battery cells. Despite considerable efforts, the development of thin SE separators with high ionic conductivities has remained a significant challenge. This paper reports the scalable production of a thin membrane comprising single-crystal SE particles that are bicontinuously embedded in a polymer matrix to form ion-conducting channels. The membrane exhibits a high ionic conductivity of 6.0 × 10−4 S cm−1 with remarkably low activation energy (20-times greater than that of current membranes with polycrystalline SE particles), eliminating large grain boundary resistances. The high conductivity enables stable lithium metal stripping and plating, producing a homogeneous ion flow to the lithium metal. Furthermore, a lithium metal–air battery cell using the membrane demonstrates a high specific energy of 700 Wh kg−1.

Atomically thin semiconducting oxide on graphene carries a unique combination of wide band gap, high charge carrier mobility, and optical transparency, which can be widely applied for optoelectronics. However, study on the epitaxial formation and properties of oxide monolayer on graphene remains unexplored due to hydrophobic graphene surface and limits of conventional bulk deposition technique. Here, we report atomic scale study of heteroepitaxial growth and relationship of a single-atom-thick ZnO layer on graphene using atomic layer deposition. We demonstrate atom-by-atom growth of zinc and oxygen at the preferential zigzag edge of a ZnO monolayer on graphene through in situ observation. We experimentally determine that the thinnest ZnO monolayer has a wide band gap (up to 4.0 eV), due to quantum confinement and graphene-like structure, and high optical transparency. This study can lead to a new class of atomically thin two-dimensional heterostructures of semiconducting oxides formed by highly controlled epitaxial growth.

For Li-ion batteries, AlF3 coating has been known to modify the over-lithiated layered oxide (OLO) cathodes to produce stable cathodes, but during synthesis procedure, the environment of excess amount of Li metal and free-exposed oxygen may cause the formation of Al2O3 and LiF materials, separately. We investigated the possibility of separated coating formation of Al as Al2O3 and F as LiF from AlF3 using density functional theory calculation, which suggests a favorable binding affinity of both Al2O3 and LiF phases to the OLO surface to support the preferable formation of coating layer of Al2O3 and LiF. Meanwhile, we found the well-distributed surface modification with the coating layers and a small amount of AlF3 (

The composite material Li x Ni 0.25 Co 0.10 Mn 0.65 O (3.4 + x) / 2 (x = 1.6, 1.4, 1.2, 1.0, 0.8) were synthesized and characterized for their structural, morphological, and performance as cathode materials in Li-ion batteries. The Rietveld refinement results indicate the presence of two phases at high lithium levels (x = 1.6 and 1.4): Li 2 MnO 3 ( C 2/ m ) and Li M O 2 ( M Ni, Co, Mn) ( R 3¯ m ); the latter contains Ni 2 + and Ni 3 + . At low lithium levels (x = 1.2, 1.0, and 0.8) an additional spinel phase Li M 2 O 4 ( Fd 3¯ m ) emerges, which is known to affect the electrochemical performance of the oxide. Structural analysis reveals that the spinel phase contains mixed transition metals Ni, Co, and Mn as [Li + ,Co 2 + ][Ni 2 + ,Co 3 + ,Mn 4 + ] 2 O 4 . A low lithium level is found to induce primary particle growth, as well as Co and Ni segregation within the secondary particles. These results are expected to contribute to material optimization and commercialization of lithium-rich oxide cathodes.

Despite the power of far-field super-resolution microscopies for three-dimensional imaging of biomolecular structures and processes, its application is challenged in dense and crowded samples and for certain surface and membrane studies. Although near-field imaging with its ability to provide intrinsic subdiffraction limited spatial resolution at any optical modality, its application to biological systems has remained limited because of the difficulties of routine operation in liquid environments. Here we demonstrate stable and sensitive near-field scanning optical microscopy (NSOM) in a liquid based on a new mechanical resonance control and an optimization of the tip length, achieving a high quality factor (>2800) force sensing of the near-field probe. Through near-field imaging of the spatial distribution of epidermal growth factor receptors (EGFRs) on the membrane of A431 cancer cells as an example, we reveal nanoscale correlations between surface EGFR and intracellular organelle structures with ∼50 nm...

Due to the importance of Ni diffusion into the electrolyte of a solid oxide fuel cell (SOFC) during the co-sintering process, we have studied the effects of Ni diffusion on the conductivity degradation and phase change of ceria-doped scandia-stabilized zirconia (ScSZ) films. To fabricate Ni-diffused ScSZ films, ScSZ tapes have been sintered by placing porous NiO plates on both sides of the tape at 1450 °C for 10 h. The time-dependent aging behavior of the Ni-diffused ScSZ film (thickness ∼27 μm) under reducing conditions has been investigated. The dissolution of Ni into the ScSZ considerably accelerates the conductivity degradation. This degradation behavior could be correlated to the phase transition promoted by Ni precipitation in the reducing atmosphere.

Van der Waals (vdW) epitaxy allows the fabrication of various heterostructures with dramatically released lattice matching conditions. This study demonstrates interface-driven stacking boundaries in WS2 using epitaxially grown tungsten disulfide (WS2 ) on wrinkled graphene. Graphene wrinkles function as highly reactive nucleation sites on WS2 epilayers; however, they impede lateral growth and induce additional stress in the epilayer due to anisotropic friction. Moreover, partial dislocation-driven in-plane strain facilitates out-of-plane buckling with a height of 1 nm to release in-plane strain. Remarkably, in-plane strain relaxation at partial dislocations restores the bandgap to that of monolayer WS2 due to reduced interlayer interaction. These findings clarify significant substrate morphology effects even in vdW epitaxy and are potentially useful for various applications involving modifying optical and electronic properties by manipulating extended 1D defects via substrate morphology control.

The recent emergence of vertically stacked van der Waals (vdW) heterostructures provides new opportunities for these materials to be employed in a wide range of novel applications. Understanding the interlayer coupling in the stacking geometries of the heterostructures and its effect on the resultant material properties is particularly important for obtaining materials with desirable properties. Here, we report that the atomic bonding between stacked layers and thereby the interlayer properties of the vdW heterostructures can be well tuned by the substrate surface defects using WS2 flakes directly grown on graphene. We show that the defects of graphene have no significant effect on the crystal structure or the quality of the grown WS2 flakes; however, they have a strong influence on the interlayer interactions between stacked layers, thus affecting the layer deformability, thermal stability, and physical and electrical properties. Our experimental and computational investigations also reveal that WS2 flakes grown on graphene defects form covalent bonds with the underlying graphene via W atomic bridges (i.e., formation of larger overlapping hybrid orbitals), enabling these flakes to exhibit different intrinsic properties, such as higher conductivity and improved contact characteristics than heterostructures that have vdW interactions with graphene. This result emphasizes the importance of understanding the interlayer coupling in the stacking geometries and its correlation effect for designing desirable properties.

With the acceleration of the scaling down of integrated circuits, it has become very challenging to fabricate a metal-insulator-metal (MIM) capacitor with a high capacitance density and low leakage current for nanoscale dynamic random access memory. Yttria-stabilized-zirconia (YSZ) thin films, one of the insulators in the constitution of MIM capacitors, have been reported to have various crystal structures from the monoclinic phase to the cubic phase according to different Y doping levels. The electrical characteristics depend on the crystal structure of the YSZ thin film. Here, we report the local crystallization of YSZ thin films via Joule heating and the leakage current induced during in situ transmission electron microscopy biasing tests. We studied the crystallization process and the increase in the leakage current using experimental and simulation results. It is important to understand the relationship between the crystallinity and electrical properties of YSZ thin films in MIM capacitors.

Hydroxyapatite (HA) coating on titanium dioxide (TiO2) nanotubular surface has been developed to complement the defects of both TiO2 and HA. A sol-gel processing technique was used to coat HA on TiO2 nanotubular surface. All the titanium discs were blasted with resorbable blast media (RBM). RBM-blasted Ti surface, anodized Ti surface, and sol-gel HA coating on the anodized Ti surface were prepared. The characteristics of samples were observed using scanning electron microscopy and X-ray photoemission spectroscopy. Biologic responses were evaluated with human osteosarcoma MG63 cells in vitro. The top of the TiO2 nanotubes was not completely covered by HA particles when the coating time was less than 60 sec. It was demonstrated the sol-gel derived HA film was well-crystallized and this enhanced biologic responses in early stage cell response.

The oxygen permeation flux of dual-phase membranes, Ce0.9Gd0.1O2-δ-La0.7Sr0.3MnO3±δ (GDC/LSM), has been systematically studied as a function of their LSM content, thickness, and coating material. The electronic percolation threshold of this GDC/LSM membrane occurs at about 20 vol % LSM. The coated LSM20 (80 vol % GDC, 20 vol % LSM) dual-phase membrane exhibits a maximum oxygen flux of 2.2 mL·cm(-2)·min(-1) at 850 °C, indicating that to enhance the oxygen permeation flux, the LSM content should be adjusted to the minimum value at which electronic percolation is maintained. The oxygen ion conductivity of the dual-phase membrane is reliably calculated from oxygen flux data by considering the effects of surface oxygen exchange. Thermal cycling tests confirm the mechanical stability of the membrane. Furthermore, a dual-phase membrane prepared here with a cobalt-free coating remains chemically stable in a CO2 atmosphere at a lower temperature (800 °C) than has previously been achieved.

Direct contacts of a metal with atomically thin two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors have been found to suppress device performance by producing a high contact resistance. NbS2 is a 2D TMDC and a conductor. It is expected to form ohmic contacts with 2D semiconductors because of its high work function and the van der Waals interface it forms with the semiconductor, with such an interface resulting in weak Fermi level pinning. Despite the usefulness of NbS2 as an electrode, previous synthesis methods could not control the thickness, uniformity, and shape of the NbS2 film and hence could not find practical applications in electronics. Here, we report a patternable method for carrying out the synthesis of NbS2 films in which the number of NbS2 layers formed over a large area was successfully controlled, which is necessary for the production of customized electrodes. The synthesized NbS2 films were shown to be highly transparent and uniform in thickness and conductivity over the large area. Furthermore, the synthesized NbS2 showed half the contact resistance than did the molybdenum metal in MoS2 field effect transistors (FETs) on a large transparent quartz substrate. The MoS2 device with NbS2 showed an electron mobility as high as 12.7 cm2 V-1 s-1, which was three times higher than that found for the corresponding molybdenum-contacted MoS2 device. This result showed the high potential of the NbS2 thin film as a transparent electrode for 2D transition metal dichalcogenide (TMDC) semiconductors with low contact resistance.

Following the celebrated discovery of graphene, considerable attention has been directed toward the rich spectrum of properties offered by van der Waals crystals. However, studies have been largely limited to their 2D properties due to lack of 1D structures. Here, the growth of high-yield, single-crystalline 1D nanobelts composed of transition metal ditellurides at low temperatures (T ≤ 500 °C) and in short reaction times (t ≤ 10 min) via the use of tellurium-rich eutectic metal alloys is reported. The synthesized semimetallic 1D products are highly pure, stoichiometric, structurally uniform, and free of defects, resulting in high electrical performances. Furthermore, complete compositional tuning of the ternary ditelluride nanobelts is achieved with suppressed phase separation, applicable to the creation of unprecedented low-dimensional materials/devices. This approach may inspire new growth/fabrication strategies of 1D layered nanostructures, which may offer unique properties that are not available in other materials.

The development of a method for synthesizing granulated silicon oxide nanoparticles (SiOx NPG) via a thermal plasma and water granulation process and determination of the optimum stoichiometry of silicon oxide (SiOx) for achieving high electrochemical performance of an anode based on the developed material are presented herein. The structure of the SiOx NPGs was confirmed by means of X-ray fluorescence, transmission electron microscopy, and X-ray diffraction. A high initial capacity of ∼1196 mA·h·g-1 was achieved using the fabricated SiOx anode with x ∼1.06, giving rise to a Coulombic efficiency of 75% after the first cycle. Further combination of SiOx with graphite (3 wt%) for use as an anode gave rise to high capacity (397 mA·h·g-1) and a very high Coulombic efficiency of 99.99% after 200 cycles. The physical properties of the synthesized materials were investigated based on micrometric analysis. On the basis of the volume expansion and cycle capacity, the optimal oxygen ratio of SiOx was determined to be x ∼1.06.