Carbon Nanotubes as a Solid-State Electron Mediator for Visible-Light-Driven Z-Scheme Overall Water Splitting.

So-called Z-scheme systems, which typically comprise an H2 evolution photocatalyst (HEP), an O2 evolution photocatalyst (OEP), and an electron mediator, represent a promising approach to solar hydrogen production via photocatalytic overall water splitting (OWS). The electron mediator transferring photogenerated charges between the HEP and OEP governs the performance of such systems. However, existing electron mediators suffer from low stability, corrosiveness to the photocatalysts, and parasitic light absorption. In the present work, carbon nanotubes (CNTs) were shown to function as an effective solid-state electron mediator in a Z-scheme OWS system. Based on the high stability and good charge transfer characteristics of CNTs, this system exhibited superior OWS performance compared with other systems using more common electron mediators. The as-constructed system evolved stoichiometric amounts of H2 and O2 at near-ambient pressure with a solar-to-hydrogen energy conversion efficiency of 0.15%. The OWS reaction was also promoted in the case that this CNT-based Z-scheme system was immobilized on a substrate. Hence, CNTs are a viable electron mediator material for large-scale Z-scheme OWS systems.

Three-dimensional assembly of multiwalled carbon nanotubes for creating a robust electron-conducting network in silicon-carbon microsphere-based electrodes.

We present a strategic approach to improve the cycle performance of a polymeric binder-free anode based on nano-Si@C microspheres by incorporating a multiwalled carbon nanotubes (MW-CNTs) network and performing carbodiimide-based condensation coupling to form a robust molecular-junction between MW-CNTs and nano-Si@C microspheres. Field-emission scanning electron microscopy reveals that one-dimensional MW-CNTs homogeneously wrapped the individual Si@C microspheres and they interwove through the intergranular nanospace. The incorporation of amide bonds at the junction primarily contributes to the stabilization and reinforcement of the hybrid electrodes. Their reversible capacity after 50 cycles with 0.5 A g-1 was significantly improved from 81 mAh·g-1 to 520 mAh·g-1. Such robustness associated with the supramolecularly assembled MW-CNTs is expected to facilitate electron conductivity and mass transfer kinetics, leading to enhanced electrochemical performance of the Si@C anode.

Waterproof molecular monolayers stabilize 2D materials.

Two-dimensional van der Waals materials have rich and unique functional properties, but many are susceptible to corrosion under ambient conditions. Here we show that linear alkylamines n-C m H2m+1NH2, with m = 4 through 11, are highly effective in protecting the optoelectronic properties of these materials, such as black phosphorus (BP) and transition-metal dichalcogenides (TMDs: WS2, 1T'-MoTe2, WTe2, WSe2, TaS2, and NbSe2). As a representative example, n-hexylamine (m = 6) can be applied in the form of thin molecular monolayers on BP flakes with less than 2-nm thickness and can prolong BP's lifetime from a few hours to several weeks and even months in ambient environments. Characterizations combined with our theoretical analysis show that the thin monolayers selectively sift out water molecules, forming a drying layer to achieve the passivation of the protected 2D materials. The monolayer coating is also stable in air, H2 annealing, and organic solvents, but can be removed by certain organic acids.

New Insight for Surface Chemistries in Ultra-thin Self-assembled Monolayers Modified High-voltage Spinel Cathodes.

The electrochemical properties of the interface between the spinel LiNi0.5Mn1.5O4-δ (LNMO4-δ) cathodes and ethylene carbonate-dimethyl carbonate (EC-DMC) electrolyte containing 1 M of LiPF6 have been investigated to achieve high-voltage durability of LNMO4-δ/graphite full cells. Coating the LNMO4-δ crystal surface by a fluoroalkylsilane self-assembled monolayer with a thickness below 2 nm resulted in a capacity retention of 94% after 100 cycles at a rate of 1 C and suppression of capacity fading for both the cathode and anode of the full cell. The observed effect is likely caused by the inhibited oxidative decomposition of EC-DMC electrolyte and vinylene carbonate (VC) species at the LNMO4-δ crystal surface and formation of a stable VC solid electrolyte interface near the anode. Moreover, the results obtained via photoelectron spectroscopy and density-functional calculations revealed that the increase in the work function of the LNMO4-δ crystal surface due to the formation of Si-O-Mn species primary contributed to the inhibition of the oxidative decomposition of the electrolyte and VC molecules at the cathode/electrolyte interface.

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate.

In this work, we demonstrate the direct growth of cubic Li5La3Nb2O12 crystal layer on the LiCoO2 substrate through the conversion of ultra-thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with Σ3 (2-1-1) = (1-21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb2O5 thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries.

We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4-δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4-δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn(3+) from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF.

Coherent diffraction imaging analysis of shape-controlled nanoparticles with focused hard X-ray free-electron laser pulses.

We report the first demonstration of the coherent diffraction imaging analysis of nanoparticles using focused hard X-ray free-electron laser pulses, allowing us to analyze the size distribution of particles as well as the electron density projection of individual particles. We measured 1000 single-shot coherent X-ray diffraction patterns of shape-controlled Ag nanocubes and Au/Ag nanoboxes and estimated the edge length from the speckle size of the coherent diffraction patterns. We then reconstructed the two-dimensional electron density projection with sub-10 nm resolution from selected coherent diffraction patterns. This method enables the simultaneous analysis of the size distribution of synthesized nanoparticles and the structures of particles at nanoscale resolution to address correlations between individual structures of components and the statistical properties in heterogeneous systems such as nanoparticles and cells.

Fundamental research on the label-free detection of protein adsorption using near-infrared light-responsive plasmonic metal nanoshell arrays with controlled nanogap.

In this work, we focused on the label-free detection of simple protein binding using near-infrared light-responsive plasmonic nanoshell arrays with a controlled interparticle distance. The nanoshell arrays were fabricated by a combination of colloidal self-assembly and subsequent isotropic helium plasma etching under atmospheric pressure. The diameter, interparticle distance, and shape of nanoshells can be tuned with nanometric accuracy by changing the experimental conditions. The Au, Ag, and Cu nanoshell arrays, having a 240-nm diameter (inner, 200-nm polystyrene (PS) core; outer, 20-nm metal shell) and an 80-nm gap distance, exhibited a well-defined localized surface plasmon resonance (LSPR) peak at the near-infrared region. PS@Au nanoshell arrays showed a 55-nm red shift of the maximum LSPR wavelength of 885 nm after being exposed to a solution of bovine serum albumin (BSA) proteins for 18 h. On the other hand, in the case of Cu nanoshell arrays before/after incubation to the BSA solution, we found a 30-nm peak shifting. We could evaluate the difference in LSPR sensing performance by changing the metal materials.

The adsorption mechanism of titanium-binding ferritin to amphoteric oxide.

We investigated the origin of selective adsorption of titanium-binding ferritin (TBF), the outer surface of which is genetically modified with titanium-binding peptides (TBPs). By varying pH conditions (7-9), TBF adsorption behavior onto amphoteric and acidic oxide substrates was observed using atomic force microscopy, and the zeta potential of substrates was measured. This suggests that a TBP interacted with local charges such as -O(-), -OH(+), and -OH(2)(+) on substrates regardless of the constituent elements of the substrate, which makes it possible for TBF to adsorb on TiO(X), ZrO(2), Fe(2)O(3), and SiO(2) substrates despite the presence of an overall electrostatic repulsive force between TBF and the substrates. This also suggests that a surfactant, TWEEN20, can completely hamper attractive interaction between TBF and acidic oxide, but amphoteric oxide can withstand TWEEN20 interference.

Simple and versatile route to high yield face-to-face dimeric assembly of Ag nanocubes and their surface plasmonic properties.

We have demonstrated the higher yield dimerization of single-crystalline Ag nanocubes through preciously controlled face-selective functionalization. With the achievement of the higher yield dimerization, we could thus observe some interesting optical properties of the dimer. Both experimental and theoretical studies revealed that the 50-nm-diameter Ag nanocubes dimers with a ca. 3.3 nm gap at their junction exhibited two plasmon peaks centered at 446 nm and 600 nm, which contributed to transverse and longitudinal plasmon resonances, respectively. Elctromagnetic calculations based on the FDTD method clearly showed that a greater enhancement of the local field occurred, with an average amplitude of the electric field of 22, at the fractal space between the aggregated Ag nanocubes when the dimer was illuminated under longitudinally polarized light.

Improvement in thickness uniformity of thick SOI by numerically controlled local wet etching.

Silicon-on-insulator (SOI) wafers are promising semiconductor materials for high-speed LSIs, low-power-consumption electric devices and micro electro mechanical systems (MEMS). The thickness distribution of an SOI causes the variation of threshold voltage in electronic devices manufactured on the SOI wafer. The thickness distribution of a thin SOI, which is manufactured by applying a smart cut technique, is comparatively uniform. On the other hand, a thick SOI has a large thickness distribution because a bonded wafer is thinned by conventional grinding and polishing. For a thick SOI wafer with a thickness of 1 microm, it is required that the tolerance of thickness variation is less than 50 nm. However, improving the thickness uniformity of a thick SOI layer to a tolerance of +/- 5% is difficult by conventional machining because of the fundamental limitations of these techniques. We have developed numerically controlled local wet etching (NC-LWE) technique as a novel deterministic subaperture figuring and finishing technique, which utilizes a localized chemical reaction between the etchant and the surface of the workpiece. We demonstrated an improvement in the thickness distribution of a thick SOI by NC-LWE using an HF/HNO3 mixture, and thickness variation improved from 480 nm to 200 nm within a diameter of 170 mm.

Finishing of AT-cut quartz crystal wafer with nanometric thickness uniformity by pulse-modulated atmospheric pressure plasma etching.

Quartz resonator is a very important device to generate a clock frequency for information and telecommunication system. Improvement of the productivity of the quartz resonator is always required because a huge amount of the resonator is demanded for installing to various electronic devices. Resonance frequency of the quartz resonator is decided by the thickness of the quartz crystal wafer. Therefore, it is necessary to uniform the thickness distribution of the wafer with nanometric level. We have proposed the improvement technique of the thickness distribution of the quartz crystal wafer by numerically controlled correction using atmospheric pressure plasma which is non-contact and chemical removal technique. Heating effects of the quartz wafer in the removal rate and the correction accuracy were investigated. The heating of the substrate and compensate of the scanning speed of the worktable according to the variation of the surface temperature enabled an increase of 50% in the etching rate and 10-nanometric-level accuracy in the correction of the thickness distribution of the quartz wafer, respectively.

Fabrication of discrete polystyrene nanoparticle arrays with controllable their structural parameters.

We have demonstrated the fabrication of two-dimensionally periodic non-close packed arrays of spherical polystyrene nanoparticles with controllable their structural parameters including diameter and interpartcile distance. The principle of this procedure relies on stepwise integration of spin-coat-assisted colloidal self-assembly of the single layer of close-packed polystyrene nanoparticle on a substrate, and subsequent etching of the particle under atmospheric pressure helium plasma. The plasma process converted the close-packed nanoparticle array into non-close-packed arrangement remaining with unchanged their original spherical shape and periodicity. Owing to the etching process underwent isotropically, the structural parameters could be controlled with nanometric accuracy by the treatment time. The etching rate strongly depended on the working pressure conditions, and the etching rate under 250 Torr was ca. 3 times faster than that of the 760 Torr. The effects of the working pressure indicated the neutral helium radicals and photons diffused from the plasma might be primarily responsible for the etching.

Three-dimensional electron density mapping of shape-controlled nanoparticle by focused hard X-ray diffraction microscopy.

Coherent diffraction microscopy using highly focused hard X-ray beams allows us to three-dimensionally observe thick objects with a high spatial resolution, also providing us with unique structural information, i.e., electron density distribution, not obtained by X-ray tomography with lenses, atom probe microscopy, or electron tomography. We measured high-contrast coherent X-ray diffraction patterns of a shape-controlled Au/Ag nanoparticle and successfully reconstructed a projection and a three-dimensional image of the nanoparticle with a single pixel (or a voxel) size of 4.2 nm in each dimension. The small pits on the surface and a hollow interior were clearly visible. The Au-rich regions were identified based on the electron density distribution, which provided insight into the formation of Au/Ag nanoboxes.

Highly efficient damage-free correction of thickness distribution of quartz crystal wafers by atmospheric pressure plasma etching.

A new finishing method was developed to correct the thickness distribution of a quartz crystal wafer by the numerically controlled scanning of a localized atmospheric pressure plasma. The thickness uniformity level of a commercially available AT-cut quartz crystal wafer was improved to less than 50 nm without any subsurface damage by applying one correction process. Furthermore, applying a pulse-modulated plasma markedly decreased the correction time of the thickness distribution without breaking the quartz crystal wafer by thermal stress.

Figuring of plano-elliptical neutron focusing mirror by local wet etching.

Local wet etching technique was proposed to fabricate high-performance aspherical mirrors. In this process, only the limited area facing to the small nozzle is removed by etching on objective surface. The desired objective shape is deterministically fabricated by performing the numerically controlled scanning of the nozzle head. Using the technique, a plano-elliptical mirror to focus the neutron beam was successfully fabricated with the figure accuracy of less than 0.5 microm and the focusing gain of 6. The strong and thin focused neutron beam is expected to be a useful tool for the analyses of various material properties.