Exploring dopant effects in stannic oxide nanoparticles for CO2 electro-reduction to formate.

The electrosynthesis of formate from CO2 can mitigate environmental issues while providing an economically valuable product. Although stannic oxide is a good catalytic material for formate production, a metallic phase is formed under high reduction overpotentials, reducing its activity. Here, using a fluorine-doped tin oxide catalyst, a high Faradaic efficiency for formate (95% at 100 mA cm-2) and a maximum partial current density of 330 mA cm-2 (at 400 mA cm-2) is achieved for the electroreduction of CO2. Furthermore, the formate selectivity (≈90%) is nearly constant over 7 days of operation at a current density of 100 mA cm-2. In-situ/operando spectroscopies reveal that the fluorine dopant plays a critical role in maintaining the high oxidation state of Sn, leading to enhanced durability at high current densities. First-principle calculation also suggests that the fluorine-doped tin oxide surface could provide a thermodynamically stable environment to form HCOO* intermediate than tin oxide surface. These findings suggest a simple and efficient approach for designing active and durable electrocatalysts for the electrosynthesis of formate from CO2.

Bottom-Up Evolution of Diamond-Graphite Hybrid Two-Dimensional Nanostructure: Underlying Picture and Electrochemical Activity.

The diamond-graphite hybrid thin film with low-dimensional nanostructure (e.g., nitrogen-included ultrananocrystalline diamond (N-UNCD) or the alike), has been employed in many impactful breakthrough applications. However, the detailed picture behind the bottom-up evolution of such intriguing carbon nanostructure is far from clarified yet. Here, the authors clarify it, through the concerted efforts of microscopic, physical, and electrochemical analyses for a series of samples synthesized by hot-filament chemical vapor deposition using methane-hydrogen precursor gas, based on the hydrogen-dependent surface reconstruction of nanodiamond and on the substrate-temperature-dependent variation of the growth species (atomic hydrogen and methyl radical) concentration near substrate. The clarified picture provides insights for a drastic enhancement in the electrochemical activities of the hybrid thin film, concerning the detection of important biomolecule, that is, ascorbic acid, uric acid, and dopamine: their limits of detections are 490, 35, and 25 nm, respectively, which are among the best of the all-carbon thin film electrodes in the literature. This work also enables a simple and effective way of strongly enhancing AA detection.

Random nanohole arrays and its application to crystalline Si thin foils produced by proton induced exfoliation for solar cells.

We report high efficiency cell processing technologies for the ultra-thin Si solar cells based on crystalline Si thin foils (below a 50 µm thickness) produced by the proton implant exfoliation (PIE) technique. Shallow textures of submicrometer scale is essential for effective light trapping in crystalline Si thin foil based solar cells. In this study, we report the fabrication process of random Si nanohole arrays of ellipsoids by a facile way using low melting point metal nanoparticles of indium which were vacuum-deposited and dewetted spontaneously at room temperature. Combination of dry and wet etch processes with indium nanoparticles as etch masks enables the fabrication of random Si nanohole arrays of an ellipsoidal shape. The optimized etching processes led to effective light trapping nanostructures comparable to conventional micro-pyramids. We also developed the laser fired contact (LFC) process especially suitable for crystalline Si thin foil based PERC solar cells. The laser processing parameters were optimized to obtain a shallow LFC contact in conjunction with a low contact resistance. Lastly, we applied the random Si nanohole arrays and the LFC process to the crystalline Si thin foils (a 48 µm thickness) produced by the PIE technique and achieved the best efficiency of 17.1% while the planar PERC solar cell without the Si nanohole arrays exhibit 15.6%. Also, we demonstrate the ultra-thin wafer is bendable to have a 16 mm critical bending radius.

Strong chromate-adsorbent based on pyrrolic nitrogen structure: An experimental and theoretical study on the adsorption mechanism.

Chromate is considered a toxic contaminant in various water sources because it poses a risk to animal and human health. To meet the stringent limits for chromium in water and wastewater, pyrrolic nitrogen structure was investigated as a chromate adsorbent for aqueous solutions, employing a polypyrrole coating on carbon black. The characteristics of the adsorbent were analyzed by high-resolution transmission electron microscopy, energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Chromate was adsorbed as both Cr(III) and Cr(VI). The chromate adsorption capacity increased (from 50.84 to 174.81 mg/g) with increasing amounts of pyrrole monomers (from 50 to 86%) in the adsorbent. The adsorption capacity was well-correlated with the pyrrolic nitrogen content (from 2.06 to 6.57 at%) in the adsorbent, rather than other types of nitrogen. The optimized adsorption capacity (174.81 mg/g in the equilibrium batch experiment and 211.10 mg/g at an initial pH of 3) was far superior to those of conventional adsorbents. We investigated the mechanism behind this powerful chromate adsorption on pyrrolic nitrogen via physical/chemical analyses of the pH-dependent adsorption behavior, supported by first-principles calculation based on density functional theory. We found that Cr(III) and Cr(VI) adsorption followed different reaction paths. Cr(III) adsorption occurred in two sequential steps: 1) A Jones oxidation reaction (JOR)-like reaction of Cr(VI) with pyrrolic N that generates Cr(III), and 2) Cr(III) adsorption on the deprotonated pyrrolic N through Cr(III)-N covalent bonding. Cr(VI) adsorption followed an alternative path: hydrogen-bonding to the deprotonation-free pyrrolic N sites. The pH-dependent fractional deprotonation of the pyrrolic N sites by the JOR-like reaction in the presence of chromate played an important role in the adsorption.

Scalable excitatory synaptic circuit design using floating gate based leaky integrators.

We propose a scalable synaptic circuit realizing spike timing dependent plasticity (STDP)-compatible with randomly spiking neurons. The feasible working of the circuit was examined by circuit simulation using the BSIM 4.6.0 model. A distinguishable feature of the circuit is the use of floating-gate integrators that provide the compact implementation of biologically plausible relaxation time scale. This relaxation occurs on the basis of charge tunneling that mainly relies upon area-independent tunnel barrier properties (e.g. barrier width and height) rather than capacitance. The circuit simulations feature (i) weight-dependent STDP that spontaneously limits the synaptic weight growth, (ii) competitive synaptic adaptation within both unsupervised and supervised frameworks with randomly spiking neurons. The estimated power consumption is merely 34 pW, perhaps meeting one of the most crucial principles (power-efficiency) of neuromorphic engineering. Finally, a means of fine-tuning the STDP behavior is provided.

Fabrication of parabolic Si nanostructures by nanosphere lithography and its application for solar cells.

We demonstrated fabrication of a parabola shaped Si nanostructures of various periods by combined approach of nanosphere lithography and a single step CF4/O2 reactive ion etch (RIE) process. Silica nanosphere monolayers in a hexagonal array were well deposited by a solvent controlled spin coating technique based on binary organic solvents. We showed numerically that a parabolic Si nanostructure of an optimal period among various-shaped nanostructures overcoated with a dielectric layer of a 70 nm thickness provide the most effective antireflection. As the simulation results as a design guide, we fabricated the parabolic Si nanostructures of a 520 nm period and a 300 nm height exhibiting the lowest weighted reflectance of 2.75%. With incorporation of such parabolic Si nanostructures, a damage removal process for 20 sec and SiNx antireflection coating of a 70 nm thickness, the efficiency of solar cells increased to 17.2% while that of the planar cells without the nanostructures exhibited 16.2%. The efficiency enhancement of the cell with the Si nanostructures was attributed to the improved photocurrents arising from the broad spectral antireflection which was confirmed by the external quantum efficiency (EQE) measurements.

Chromate adsorption mechanism on nanodiamond-derived onion-like carbon.

The onion-like carbon (OLC) was prepared as adsorbent and tested for the removal of chromate ions from aqueous solutions. The OLC was thermally derived from nanodiamond by vacuum annealing at 1000-2000°C. An investigation was conducted the chromate adsorption mechanism of OLC, by analysing the temperature-dependent evolution of the various oxygen-carbon bonds and the chemisorbed water by X-ray photo electron spectroscopy, as well as by the first principle calculation of the bond energies for relevant bond configurations. The present work demonstrated the importance of the carbon-oxygen bond type and carbon dangling bonds for chromate adsorption, as well as for other anionic heavy metals adsorbed from wastewater and sewage.

Inherently-Forced Tensile Strain in Nanodiamond-Derived Onion-like Carbon: Consequences in Defect-Induced Electrochemical Activation.

We analyzed the nanodiamond-derived onion-like carbon (OLC) as function of synthesis temperature (1000~1400 °C), by high-resolution electron microscopy, electron energy loss spectroscopy, visible-Raman spectroscopy, ultraviolet photoemission spectroscopy, impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The temperature dependences of the obtained properties (averaged particle size, tensile strain, defect density, density of states, electron transfer kinetics, and electrochemical oxidation current) unanimously coincided: they initially increased and saturated at 1200 °C. It was attributed to the inherent tensile strains arising from (1) the volume expansion associated with the layer-wise diamond-to-graphite transformation of the core, which caused forced dilation of the outer shells during their thermal synthesis; (2) the extreme curvature of the shells. The former origin was dominant over the latter at the outermost shell, of which the relevant evolution in defect density, DOS and electron transfer kinetics determined the electrochemical performances. In detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) using the OLC as electrode, their oxidation peak currents were enhanced by factors of 15~60 with annealing temperature. Their limit of detection and the linear range of detection, in the post-treatment-free condition, were as excellent as those of the nano-carbon electrodes post-treated by Pt-decoration, N-doping, plasma, or polymer.

A comprehensive study on atomic layer deposition of molybdenum sulfide for electrochemical hydrogen evolution.

Atomic layer deposition (ALD) has emerged as an efficient method to design and prepare catalysts with atomic precision. Here, we report a comprehensive study on ALD of molybdenum sulfide (MoSx) for an electrocatalytic hydrogen evolution reaction. By using molybdenum hexacarbonyl and dimethyldisulfide as the precursors of Mo and S, respectively, the MoSx catalysts are grown at 100 °C on porous carbon fiber papers (CFPs). The ALD process results in the growth of particle-like MoSx on the CFP due to the lack of adsorption sites, and its crystallographic structure is a mixture of amorphous and nano-crystalline phases. In order to unveil the intrinsic activity of the ALD-MoSx, the exchange current densities, Tafel slopes, and turnover frequencies of the catalysts grown under various ALD conditions have been investigated by considering the fractional surface coverage of MoSx on the CFP and catalytically-active surface area. In addition, the ALD-MoSx/CFP catalysts exhibit excellent catalytic stability due to the strong adhesion of MoSx on the CFP and the mixed phase.

Photocurrent enhancements of organic solar cells by altering dewetting of plasmonic Ag nanoparticles.

Incorporation of metal nanoparticles into active layers of organic solar cells is one of the promising light trapping approaches. The size of metal nanoparticles is one of key factors to strong light trapping, and the size of thermally evaporated metal nanoparticles can be tuned by either post heat treatment or surface modification of substrates. We deposited Ag nanoparticles on ITO by varying nominal thicknesses, and post annealing was carried out to increase their size in radius. PEDOT: PSS was employed onto the ITO substrates as a buffer layer to alter the dewetting behavior of Ag nanoparticles. The size of Ag nanoparticles on PEDOT: PSS were dramatically increased by more than three times compared to those on the ITO substrates. Organic solar cells were fabricated on the ITO and PEDOT: PSS coated ITO substrates with incorporation of those Ag nanoparticles, and their performances were compared. The photocurrents of the cells with the active layers on PEDOT: PSS with an optimal choice of the Ag nanoparticles were greatly enhanced whereas the Ag nanoparticles on the ITO substrates did not lead to the photocurrent enhancements. The origin of the photocurrent enhancements with introducing the Ag nanoparticles on PEDOT: PSS are discussed.

Multiprotocol-induced plasticity in artificial synapses.

We suggest a 'universal' electrical circuit for the realization of an artificial synapse that exhibits long-term plasticity induced by different protocols. The long-term plasticity of the artificial synapse is basically attributed to the nonvolatile resistance change of the bipolar resistive switch in the circuit. The synaptic behaviour realized by the circuit is termed 'universal' inasmuch as (i) the shape of the action potential is not required to vary so as to implement different plasticity-induction behaviours, activity-dependent plasticity (ADP) and spike-timing-dependent plasticity (STDP), (ii) the behaviours satisfy several essential features of a biological chemical synapse including firing-rate and spike-timing encoding and unidirectional synaptic transmission, and (iii) both excitatory and inhibitory synapses can be realized using the same circuit but different diode polarity in the circuit. The feasibility of the suggested circuit as an artificial synapse is demonstrated by conducting circuit calculations and the calculation results are introduced in comparison with biological chemical synapses.

Silicon nanodisk array design for effective light trapping in ultrathin c-Si.

The use of ultrathin c-Si (crystalline silicon) wafers thinner than 20 µm for solar cells is a very promising approach to realize dramatic reduction in cell cost. However, the ultrathin c-Si requires highly effective light trapping to compensate optical absorption reduction. Conventional texturing in micron scale is hardly applicable to the ultrathin c-Si wafers; thus, nano scale texturing is demanded. In general, nanotexturing is inevitably accompanied by surface area enlargements, which must be minimized in order to suppress surface recombination of minority carriers. In this study, we demonstrate using optical simulations that periodic c-Si nanodisk arrays of short heights less than 200 nm and optimal periods are very useful in terms of light trapping in the ultrathin c-Si wafers while low surface area enlargements are maintained. Double side texturing with the nanodisk arrays leads to over 90% of the Lambertian absorption limit while the surface area enlargement is kept below 1.5.

Novel aspect in grain size control of nanocrystalline diamond film for thin film waveguide mode resonance sensor application.

Nanocrystalline diamond (NCD) thin film growth was systematically investigated for application for the thin film waveguide mode resonance sensor. The NCD thin film was grown on the Si wafer or on the SiO2-coated sapphire substrate using the hot filament chemical vapor deposition (HFCVD). The structural/optical properties of the samples were characterized by the high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS), near edge X-ray absorption fine structure (NEXAFS), X-ray diffraction (XRD), and ultraviolet-visible (UV-vis) spectroscopy. The waveguide modes of the NCD layer were studied by prism coupler technique using laser (wavelength: 632.8 nm) with varying incident angle. A novel aspect was disclosed in the grain size dependence on the growth temperature at the relatively low methane concentration in the precursor gas, which was important for optical property: the grain size increased with decreasing growth temperature, which was contrary to the conventional knowledge prevailing in the microcrystalline diamond (MCD) domain. We have provided discussions to reconcile such observation. An optical waveguide mode resonance was demonstrated in the visible region using the microstructure-controlled transparent NCD thin film waveguide, which provided a strong potential for the waveguide mode resonance sensor applications.

Optical design of transparent metal grids for plasmonic absorption enhancement in ultrathin organic solar cells.

Transparent metal grid combining with plasmonic absorption enhancement is a promising replacement to indium tin oxide thin films. We numerically demonstrate metal grids in one or two dimension lead to plasmonic absorption enhancements in ultrathin organic solar cells. In this paper, we study optical design of metal grids for plasmonic light trapping and identify different plasmonic modes of the surface plasmon polaritons excited at the interfaces of glass/metal grids, metal grids/active layers, and the localized surface plasmon resonance of the metal grids using numerical calculations. One dimension metal grids with the optimal design of a width and a period lead to the absorption enhancement in the ultrathin active layers of 20 nm thickness by a factor of 2.6 under transverse electric polarized light compared to the case without the metal grids. Similarly, two dimensional metal grids provide the absorption enhancement by a factor of 1.8 under randomly polarized light.

Plasmonic nanograting design for inverted polymer solar cells.

Plasmonic nanostructures for effective light trapping in a variety of photovoltaics have been actively studied. Metallic nanograting structures are one of promising architectures. In this study, we investigated numerically absorption enhancement mechanisms in inverted polymer photovoltaics with one dimensional Ag nanograting in backcontact. An optical spacer layer of TiO2, which also may act as an electron transport layer, was introduced between nanograting pillars. Using a finite-difference-time domain method and performing a modal analysis, we explored correlations between absorption enhancements and dimensional parameters of nanograting such as period as well as height and width. The optimal design of nanograting for effective light trapping especially near optical band gap of an active layer was discussed, and 23% of absorption enhancement in a random polarization was demonstrated numerically with the optimally designed nanograting. In addition, the beneficial role of the optical spacer in plasmonic light trapping was also discussed.