Experimental Formation and Mechanism Study for Super-High Dielectric Constant AlOx/TiOy Nanolaminates.

Super-high dielectric constant (k) AlOx/TiOy nanolaminates (ATO NLs) are deposited by an atomic layer deposition technique for application in next-generation electronics. Individual multilayers with uniform thicknesses are formed for the ATO NLs. With an increase in AlOx content in each ATO sublayer, the shape of the Raman spectrum has a tendency to approach that of a single AlOx layer. The effects of ATO NL deposition conditions on the electrical properties of the metal/ATO NL/metal capacitors were investigated. A lower deposition temperature, thicker ATO NL, and lower TiOy content in each ATO sublayer can lead to a lower leakage current and smaller loss tangent at 1 kHz for the capacitors. A higher deposition temperature, larger number of ATO interfaces, and higher TiOy content in each ATO sublayer are important for obtaining higher k values for the ATO NLs. With an increase in resistance in the capacitors, the ATO NLs vary from semiconductors to insulators and their k values have a tendency to decrease. For most of the capacitors, the capacitances reduce with increments in absolute measurement voltage. There are semi-circular shapes for the impedance spectra of the capacitors. By fitting them with the equivalent circuit, it is observed that with the increase in absolute voltage, both parallel resistance and capacitance decrease. The variation in the capacitance is explained well by a novel double-Schottky electrode contact model. The formation of super-high k values for the semiconducting ATO NLs is possibly attributed to the accumulation of charges.

Edge-of-chaos learning achieved by ion-electron-coupled dynamics in an ion-gating reservoir.

Physical reservoir computing has recently been attracting attention for its ability to substantially reduce the computational resources required to process time series data. However, the physical reservoirs that have been reported to date have had insufficient computational capacity, and most of them have a large volume, which makes their practical application difficult. Here, we describe the development of a Li+ electrolyte-based ion-gating reservoir (IGR), with ion-electron-coupled dynamics, for use in high-performance physical reservoir computing. A variety of synaptic responses were obtained in response to past experience, which were stored as transient charge density patterns in an electric double layer, at the Li+ electrolyte/diamond interface. Performance for a second-order nonlinear dynamical equation task is one order of magnitude higher than memristor-based reservoirs. The edge-of-chaos state of the IGR enabled the best computational capacity. The IGR described here opens the way for high-performance and integrated neural network devices.

Tunability of the bandgap of SnS by variation of the cell volume by alloying with A.E. elements.

We clarified that the bandgap of inorganic materials is strongly correlated with their effective coordination number (ECoN) via first-principles calculations and experimental confirmations. Tin mono-sulphide (Pnma) and germanium mono-sulphide (Pnma) were selected as model cases since these materials successively alter the ECoN as the cell volume changes and show an uncommon relationship between cell volume and bandgap. Contrary to the common semiconductors, the bandgaps of SnS (Pnma) and GeS (Pnma) have a positive relationship with respect to cell volume. This unique phenomenon was explained by incorporating the concept of ECoN into the theoretical studies. The theory proposed in this study is widely applicable to semiconductors with low-symmetry structures. Further, we experimentally demonstrated that the bandgap of SnS (Pnma) can be broadly tuned by changing the unit cell volume via alloying with alkali-earth (A.E.) metals, which could allow SnS to be applied to Si-based tandem photovoltaics. Alloying with A.E. elements also stabilised Cl as an n-type donor, which enabled n-type conduction in the bandgap-widened SnS film in the SnS-based semiconductors.

Synthesis of CaSnN2 via a High-Pressure Metathesis Reaction and the Properties of II-Sn-N2 (II = Ca, Mg, Zn) Semiconductors.

A novel ternary nitride semiconductor, CaSnN2, with a layered rock-salt-type structure (R3̅m) was synthesized via a high-pressure metathesis reaction. The properties and structures of II-Sn-N2 (II = Ca, Mg, Zn) semiconductors were also systematically studied, and the differences among them were revealed by comparison. These semiconductor materials showed a rock-salt- or wurtzite-type structure depending on the combined effect of the synthetic conditions and the characteristics of the group II elements. Additionally, the rock-salt-type structures of CaSnN2 and MgSnN2 (i.e., the ambient-pressure phase) were different from those predicted using first-principles calculations. Further, on the basis of first-principles calculations and consideration of the pressure effect, the recovered CaSnN2 sample showed an R3̅m structure. CaSnN2 and MgSnN2 showed a band gap of 2.3-2.4 eV, which is suitable for overcoming the green-light-gap problem. These semiconductors also showed a strong cathode luminescence peak at room temperature, and generalized gradient approximation (GGA) calculations revealed that CaSnN2 has a direct band gap. These inexpensive and nontoxic semiconductors (II-Sn-N2 semiconductors (II = Ca, Mg, Zn)), with mid band gaps are required as pigments to replace cadmium-based materials. They can also be used in emitting devices and as photovoltaic absorbers, replacing InxGa1-xN semiconductors.

The electric double layer effect and its strong suppression at Li+ solid electrolyte/hydrogenated diamond interfaces.

The electric double layer (EDL) effect at solid electrolyte/electrode interfaces has been a key topic in many energy and nanoelectronics applications (e.g., all-solid-state Li+ batteries and memristors). However, its characterization remains difficult in comparison with liquid electrolytes. Herein, we use a novel method to show that the EDL effect, and its suppression at solid electrolyte/electronic material interfaces, can be characterized on the basis of the electric conduction characteristics of hydrogenated diamond(H-diamond)-based EDL transistors (EDLTs). Whereas H-diamond-based EDLT with a Li-Si-Zr-O Li+ solid electrolyte showed EDL-induced hole density modulation over a range of up to three orders of magnitude, EDLT with a Li-La-Ti-O (LLTO) Li+ solid electrolyte showed negligible enhancement, which indicates strong suppression of the EDL effect. Such suppression is attributed to charge neutralization in the LLTO, which is due to variation in the valence state of the Ti ions present. The method described is useful for quantitatively evaluating the EDL effect in various solid electrolytes.

Magnetic Control of Magneto-Electrochemical Cell and Electric Double Layer Transistor.

A magneto-electrochemical cell and an electric double layer transistor (EDLT), each containing diluted [Bmim]FeCl4 solution, have been controlled by applying a magnetic field in contrast to the control of conventional field effect devices by an applied electric field. A magnetic field of several hundred mT generated by a small neodymium magnet is sufficient to operate magneto-electrochemical cells, which generate an electromotive force of 130 mV at maximum. An EDLT composed of hydrogen-terminated diamond was also operated by applying a magnetic field. Although it showed reversible drain current modulation with a magnetoresistance effect of 503%, it is not yet advantageous for practical application. Magnetic control has unique and interesting characteristics that are advantageous for remote control of electrochemical behavior, the application for which conventional electrochemical devices are not well suited. Magnetic control is opening a door to new applications of electrochemical devices and related technologies.

Phosphonate-Derived Nanoporous Metal Phosphates and Their Superior Energy Storage Application.

Nanoporous nickel, aluminum, and zirconium phosphates (hereafter, abbreviated as NiP, AlP, and ZrP, respectively) with high surface areas and controlled morphology and crystallinity have been synthesized through simple calcination of the corresponding phosphonates. For the preparation of phosphonate materials, nitrilotris(methylene)triphosphonic acid (NMPA) is used as phosphorus source. The organic component in the phosphonate materials is thermally removed to form nanoporous structures in the final phosphate materials. The formation mechanism of nanoporous structures, as well as the effect of applied calcination temperatures on the morphology and crystallinity of the final phosphate materials, is carefully discussed. Especially, nanoporous NiP materials have a spherical morphology with a high surface area and can have great applicability as an electrode material for supercapacitors. It has been found that there is a critical effect of particle sizes, surface areas, and the crystallinities of NiP materials toward electrochemical behavior. Our nanoporous NiP material has superior specific capacitance, as compared to various phosphate nanomaterials reported previously. Excellent retention capacity of 97% is realized even after 1000 cycles, which can be ascribed to its high structural stability.

Ordered Mesoporous Cobalt Phosphate with Crystallized Walls toward Highly Active Water Oxidation Electrocatalysts.

A hexagonally ordered mesoporous cobalt phosphate (CoPi) material is prepared by a facile one-pot soft-templating strategy using cetyltrimethylammonium bromide template. Because of its highly accessible surface area and crystalline framework with abundant active sites, the mesoporous CoPi shows a high catalytic activity for the oxygen evolution reaction compared to previously reported noble/transition-metal and nonmetal catalysts.

Electrotactile Augmentation for Carving Guidance.

In this study, we presented an efficient and unobtrusive tactile feedback system, which is used to train dental technicians in carving tasks using a wax stick and knife. First, we developed a method for generating performance metrics using a model-based estimation of clearance angles between an object's surface and the carving blade. The calculated clearance angles are compared with desired angles obtained from expert operators. Then, angular errors are presented as tactile cues to the user's finger pads through electrical stimuli at the middle phalanx of the index finger and the thumb. Subsequently, we conducted a feasibility test with novice dental technicians, who showed improvement in initial clearance angles of carving strokes. Moreover, the results showed significant reduction in the occurrence rate of poor-carving when using the proposed system. From these results, we concluded that electrotactile augmentation can provide effective guidance for carving tasks.

Noninvasive simultaneous measurement of blood pressure and blood flow velocity for hemodynamic analysis.

We describe a noninvasive and simultaneous measurement method of beat-by-beat blood pressure and blood flow velocity waveforms in the radial artery using tonometry and Doppler flowmetry. We conducted a subjective experiment in which hold-down pressure of tonometry was controlled for determining optimal hold-down pressure and the measurement accuracy under the optimal hold-down pressure was evaluated. As a result, blood pressure and blood flow velocity could be measured simultaneously without the influence of the hold-down pressure on the blood flow velocity. It was possible to analyze hemodynamic indicators, such as wave intensity and vascular impedance, with blood pressure and blood flow using the system. The proposed system for detecting unexpected fluctuations in blood pressure and the involved mechanisms may contribute to the treatment of cardiovascular diseases.

Mesoporous Pt nanospheres with designed pore surface as highly active electrocatalyst.

A novel strategy for large-scale synthesis of shape- and size-controlled mesoporous Pt nanospheres (MPNs) through a slow reduction reaction in the presence of surfactant is reported here for the first time. The slow reduction reaction exclusively results in well-defined mesoporous architectures distinctly different from the dendritic constructions reported previously. More importantly, abundant catalytically active sites are created on the highly accessible mesoporous surfaces by the selective adsorption of bromide ions. The MPNs prepared by using the new synthetic route not only show superior electrochemical performance toward methanol oxidation reaction and oxygen reduction reaction, but also exhibit extremely high structural thermostability, which makes them promising catalysts for industrial applications.

Oxygen-Assisted Synthesis of Mesoporous Palladium Nanoparticles as Highly Active Electrocatalysts.

Mesoporous Pd nanoparticles (MPNs) enclosed by high-index facets have been successfully prepared by taking advantage of successive oxygen adsorption and desorption caused by the oxidative etching effect. The as-prepared MPNs exhibit excellent performance toward formic acid electro-oxidation, which is due to the synergetic effect between the diffusion-feasible tubular mesochannels and the high index facets.

Easy and General Synthesis of Large-Sized Mesoporous Rare-Earth Oxide Thin Films by 'Micelle Assembly'.

Large-sized (ca. 40 nm) mesoporous Er2O3 thin films are synthesized by using a triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er(3+) is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare-earth oxide (Sm2O3, Dy2O3, Tb2O3, Ho2O3, Yb2O3, and Lu2O3) thin films with potential uses in electronics and optical devices.

Shape-controlled synthesis of mesoporous iron phosphate materials with crystallized frameworks.

Herein, we report the preparation of crystalline mesoporous iron phosphate (FePO4, hereafter abbreviated as FeP) materials with 2D-plates and 1D-rods in the presence of an amphiphilic block copolymer (F127), iron nitrate, and phosphoric acid. The dimensionality of mesoporous FeP can be switched by changing the polarity of the synthetic medium.

Material Roughness Modulation via Electrotactile Augmentation.

Tactile exploration of a material's texture using a bare finger pad is a daily human activity. However, modern tactile displays do not allow users to experience the natural sensations of a material when artificial sensations are presented. We propose an electrotactile augmentation technique capable of superimposing vibrotactile sensations in a finger pad, thereby allowing the texture modulation of real materials. Users attach two stimulus electrodes to the middle phalanx of a finger and a grounded electrode at the base of the finger in order to evoke nerve activity. This paper evaluates the proposed electrotactile augmentation for roughness modulation of real materials. First, we introduce the principle of the electrotactile display, which presents artificial sensations at the finger pad. We then confirm that the perceived frequency of mechanical vibration at the finger pad can be shifted using electrotactile augmentation. Finally, we discuss a user study, wherein participants rated the roughness of real materials explored using the proposed system. Experimental results indicate that fine- and macro-roughness perceptions of real materials can be altered using electrotactile augmentation.

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry.

Polymeric micelle assembly with inorganic nanosheets for construction of mesoporous architectures with crystallized walls.

Here we propose a novel way to construct mesoporous architectures through evaporation-induced assembly of polymeric micelles with crystalline nanosheets. As a model study, we used niobate nanosheets exfoliated by the direct reaction of K4Nb6O17⋅3 H2O crystals with an aqueous solution of propylamine. The electrostatic interaction between negatively charged nanosheets and positively charged polymeric micelles enable us to form composite micelles with the nanosheets. Removal of the micelles by calcination results in robust mesoporous oxides with the original crystalline structure.

Controlled synthesis of nanoporous nickel oxide with two-dimensional shapes through thermal decomposition of metal-cyanide hybrid coordination polymers.

The urgent need for nanoporous metal oxides with highly crystallized frameworks is motivating scientists to try to discover new preparation methods, because of their wide use in practical applications. Recent work has demonstrated that two-dimensional (2D) cyanide-bridged coordination polymers (CPs) are promising materials and appropriate for this purpose (Angew. Chem. Int. Ed.- 2013, 52, 1235). After calcination, 2D CPs can be transformed into nanoporous metal oxides with a highly accessible surface area. Here, this strategy is adopted in order to form 2D nanoporous nickel oxide (NiO) with tunable porosity and crystallinity, using trisodium citrate dihydrate as a controlling agent. The presence of trisodium citrate dihydrate plays a key role in the formation of 2D nanoflakes by controlling the nucleation rate and the crystal growth. The size of the nanoflakes gradually increases by augmenting the amount of trisodium citrate dihydrate in the reaction. After heating the as-prepared CPs in air at different temperatures, nanoporous NiO can be obtained. During this thermal treatment, organic units (carbon and nitrogen) are completely removed and only the metal content remains to take part in the formation of nanoporous NiO. In the case of large-sized 2D CP nanoflakes, the original 2D flake-shapes are almost retained, even after thermal treatment at low temperature, but they are completely destroyed at high temperature because of further crystallization in the framework. Nanoporous NiO with high surface area shows significant efficiency and interesting results for supercapacitor application.

Thermal conversion of core-shell metal-organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon.

Core-shell structured ZIF-8@ZIF-67 crystals are well-designed and prepared through a seed-mediated growth method. After thermal treatment of ZIF-8@ZIF-67 crystals, we obtain selectively functionalized nanoporous hybrid carbon materials consisting of nitrogen-doped carbon (NC) as the cores and highly graphitic carbon (GC) as the shells. This is the first example of the integration of NC and GC in one particle at the nanometer level. Electrochemical data strongly demonstrate that this nanoporous hybrid carbon material integrates the advantageous properties of the individual NC and GC, exhibiting a distinguished specific capacitance (270 F·g(-1)) calculated from the galvanostatic charge-discharge curves at a current density of 2 A·g(-1). Our study not only bridges diverse carbon-based materials with infinite metal-organic frameworks but also opens a new avenue for artificially designed nanoarchitectures with target functionalities.

Finger motion capture from wrist-electrode contact resistance.

Hand motion capture is an important yet challenging topic for biomechanics and human computer interaction. We proposed a novel electrical sensing technology for capturing the finger angles from the variation of the wrist shape. The proposed device detects the signal related to the wrist-electrode contact resistances, which change according to the variation of the wrist shape accompanying finger movements. The developed sensing device consists of a wrist band, sixteen electrodes and a sensing circuit of contact resistances. We investigated the relationships between the finger angles and the system outputs by using a glove-type joint angle sensor. As a result, we confirmed high correlations of the system outputs with the finger angles for several electrodes. Therefore, we conclude that the proposed system can be used for the estimation of the finger joint angles.