Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors

The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge accumulation. Much effort has recently been devoted to the fundamental understanding and practical applications of such highly charged EDL interfaces. However, the intrinsic nature of the EDL charging, whether it is electrostatics or electrochemistry, and how to distinguish them are far from clear. Here, by combining electrical transport measurements with electrochemical impedance spectroscopy (EIS), we studied the charging mechanisms of highly charged EDL interfaces between an ionic liquid and oxide semiconductor, ZnO. The direct measure for mobile carriers from the Hall effect agreed well with that from the capacitance-voltage integration at 1 Hz, implying that the pseudocapacitance does not contribute to carrier transport at EDL interfaces. The temperature-frequency mapping of EIS was further demonstrated as a "phase diagram" to distinguish the electrostatic or electrochemical nature of such highly charged EDL interfaces with densities of up to 8 × 10(14) cm(-2), providing a guideline for electric-field-induced electronic phenomena and a simple method for distinguishing electrostatic and electrochemical charging in EDLTs not only based on a specific oxide semiconductor, ZnO, but also commonly applicable to all types of EDL interfaces with extremely high-density carrier accumulation.     

The effect of water-miscible organic solvents on the substitution reaction of Keggin-type heteropolysilicates and -germanates with vanadium(V) ion

The substitution reaction of Keggin-type polyoxometalates, [XM₁₂O₄₀]ⁿ⁻ (X = Si, Ge, P, or As; M = Mo or W), with vanadium(V) ion was investigated with cyclic voltammetry, Raman spectroscopy, and ³¹P NMR. The effect of organic solvents, such as acetonitrile (ACN), tetrahydrofuran (THF), formamide (FA), N-methylformamide (NMF), and N-methylacetoamide (NMA) on their substitution reactions was examined. In aqueous and aqueous-FA, -NMF, and -NMA solutions, the molybdenum or tungsten unit in the Keggin-anions was substituted with vanadium(V) ion to form V(V)-substituted polyoxometalates, while no substitution reaction occurred in aqueous-ACN and -THF solutions. It is suggested that this results from the relationship between the total anion charge and the permittivity of organic solvents.     

Determination of traces of palladium in stream sediment and auto catalyst by FI-ICP-OES using on-line separation and preconcentration with QuadraSil TA

A flow injection analysis (FIA) method using on-line separation and preconcentration with a novel metal scavenger beads, QuadraSil™ TA, has been developed for the ICP-OES determination of traces of palladium. QuadraSil TA contains diethylenetriamine as a functional group on spherical silica beads and shows the highest selectivity for Pd(II) at pH 1 (0.1 mol l⁻¹ hydrochloric acid) solution. An aliquot of the sample solution prepared as 0.1 mol l⁻¹ in hydrochloric acid was passed through the QuadraSil TA column. After washing the column with the carrier solution, the Pd(II) retained on the column was eluted with 0.05 mol l⁻¹ thiourea solution and the eluate was directly introduced into an ICP-OES. The proposed method was successfully applied to the determination of traces of palladium in JSd-2 stream sediment certified reference material [0.019 ± 0.001 μg g⁻¹ (n = 3); provisional value: 0.0212 μg g⁻¹] and SRM 2556 used auto catalyst certified reference material [315 ± 4 μg g⁻¹ (n = 4); certified value: 326 μg g⁻¹]. The detection limit (3σ) of 0.28 ng ml⁻¹ was obtained for 5 ml of sample solution. The sample throughputs for 5 ml and 100 μl of the sample solutions were 10 and 15 h⁻¹, respectively.     

Chemical etchant dependence of surface structure and morphology on GaN(0001) substrates

We studied the procedure of cleaning GaN(0001) substrate surfaces by wet etching and subsequent annealing in ultrahigh vacuum for two different types of freestanding GaN wafers: hydride vapor phase epitaxy (HVPE) crystal and Na flux liquid phase epitaxy (LPE) crystal wafers. A flat surface containing GaN(0001)2 × 2 reconstruction was successfully achieved on both HVPE and LPE surfaces by etching in HF and subsequent annealing at ～ 550 °C but was not achieved by etching in HCl, NaOH, and HNO₃.     

Subterranean electrical structure of Kozu-shima volcanic island, Japan

Following the electric current injection experiment carried out in 2009, a VLF-MT (Very Low Frequency Magnetotelluric) survey has been conducted in Kozu-shima Island to obtain further information on the subterranean electrical structure that might help understanding the results of our monitoring of geoelectric potentials. A number of VAN-type pre-seismic geoelectric potential anomalies were observed in 1997-2000, even showing a remarkable "Selectivity". However, similar pre-seismic anomalies were not observed during the Izu-Island volcano-seismic swarm 2000. All these observations would require extremely high degree of heterogeneity in the subterranean electrical structure of the volcanic island and its possible time changes. Several correlations between the results of this survey and the volcanic geology of the island and ground water distribution were found. Further investigation is needed for a complete explanation of the observed phenomena.     

Synthesis and lithium ion insertion/extraction properties of hollandite-type MnO2 prepared by acid digestion of Mn2O3

Single-phase specimens of α-MnO₂ (hollandite-type) and β-MnO₂ (rutile-type) were synthesized by the acid digestion of Mn₂O₃ under reflux conditions. The type of polymorph of MnO₂ products was strongly dependent on the reaction temperature, type of acid used, and its concentration. The pH titration curve of α-MnO₂ displayed a monobasic acid behavior toward Li⁺, but β-MnO₂ showed a poor ion-exchange property. In contrast, both α-MnO₂ and β-MnO₂ acted as a rechargeable active material in a liquid organic electrolyte lithium cell. The initial discharge capacities of both electrodes exceeded 200 mAh/g (cut-off voltage: 2 V). After discharge–charge repetition, the α-MnO₂ structure was still retained without structure collapse, although the β-MnO₂ structure was destroyed. These findings show that Li⁺ ions can be inserted only into the hollandite-type tunnels in α-MnO₂ and cannot diffuse the rutile-type linkages in α-MnO₂ as well as those in β-MnO₂ without structure collapse.     

Relationship between wavelength combination and signal-to-noise ratio in measuring hemoglobin concentrations using visible or near-infrared light

The signal-to-noise ratio (SNR), when using visible or near-infrared light to measure the change in hemoglobin concentration length (the product of hemoglobin concentration and optical path length in this study), depends on the wavelength combination and the analysis method. Although the SNRs increase when detected or incident optical power increases, the optical power should be limited because of safety standards. Considering these safety standards, we assumed that the total optical power was constant by using the relationship between optical power and measurement error. We investigated the theoretical estimation errors of the changes in hemoglobin concentration length using two, three, and four different wavelengths. The SNRs of the changes in hemoglobin concentration length were high when fewer wavelengths were used. These SNRs decreased when the redox state change in cytochrome oxidase was included in the analysis.     

Qubit decoherence with an initial correlation

Decoherence of a qubit system interacting with a bosonic reservoir is considered when there is at most one excitation in the whole system and there is an initial correlation with the reservoir. An exact time-evolution of the system is obtained and the effect of the initial correlation on the time-evolution is examined in detail.