Electrochemical etching process to tune the diameter of arrayed deep pores by controlling carrier collection at a semiconductor–electrolyte interface

An approach to control the diameter of high-aspect-ratio pores formed into a silicon wafer by an electrochemical etching process is reported. Hole (h⁺) was involved in the etching reaction and the collection of the h⁺ was the key factor. Artificial micro-cavities were fabricated on the silicon surface prior to the etching. The depth of the space charge region (SCR), Schottky barrier on the silicon-electrolyte interface, was adjusted regarding the depth of the micro-cavities by applied overpotential and specific resistance of the silicon wafer. The collection of h⁺ at the tip of the cavity site was widely controlled by the adjusted SCR. Consequently the electrochemically etched domain at the cavity site was actively tuned, and then high-aspect-ratio pore with the controlled diameter was formed. The diameter was tuned by the SCR depth which was controlled by the overpotential and the specific resistance. The diameter tuning mechanism worked under the mask-free condition.     

Sound velocity measurement of nuclear-ordered U2D2 solid He along the melting curve

The sound velocity of a single-domain ³He crystal was measured in the nuclear-ordered low-field phase and the paramagnetic phase along the melting curve, using 10.98 MHz longitudinal sound. The temperature dependence of the sound velocity along the melting curve was explained by a nuclear spin contribution and the molar volume change along the melting curve. By comparing the measured velocity with thermodynamic quantities, we extracted the Grüneizen constant for the exchange energy. The anisotropy of the velocity in the ordered phase was investigated for three samples and was found to be smaller than 2×10⁻⁵ in Δv/v. The attenuation coefficient of the sound was much smaller than 0.2 cm⁻¹.     

Synthesis of hydrocarbon polymers containing bulky dibenzobicyclic moiety by ROMP and their characteristic optical properties

The eight‐membered cyclic monomer, prepared by Diels–Alder reaction of 1,5‐cyclooctadiene and anthracene, polymerized via Ru‐catalyzed ring‐opening metathesis to efficiently afford high polymers (M_n up to 631,000). Unsaturated moieties in the main chain of the obtained polymer were hydrogenated with a homogeneous ruthenium catalyst in quantitative conversion, confirmed by ¹H‐NMR measurement. The self‐standing membranes were provided by casting the tetrahydrofuran solutions of both nonhydrogenated and hydrogenated polymers. The obtained membranes showed high transparency in the region of >300 nm with mechanical flexibility. Thermal gravimetric analysis revealed that both nonhydrogenated and hydrogenated polymers decomposed in two stages. The first‐stage decomposition starting at around 230 °C was caused by retro Diels–Alder reaction forming anthracene, proven by pyrolysis gas chromatography mass spectroscopy (GC‐MS) analyses. Mechanical grinding of the polymers induced the formation of anthracene in solid state, which transformed the polymer into blue‐luminescent materials under UV irradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1392–1400     

Simple Preparation of 1-Bromo-1-Trimethylsilyl-1(Z), 4-pentadiene and its Use as 4-Pentenoyl Anion Equivalent

The titled compound is easily obtained by palladium (II)-catalyzed bromoallylation of ethynyltrimethylsilane and can serve as 4-pentenoyl anion equivalent which is a valuable synthetic grouping.     

Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes

Improved methods for the preparation of methylene-bridged diphosphine ligands are described. Both enantiomers of the key intermediate tert-butylmethylphosphine–borane were prepared via resolution or by the conversion of one enantiomer into the opposite enantiomer. The precursor borane complexes of bis(tert-butylmethylphosphino)methane (t-Bu-MiniPHOS), bis((1,1,3,3-tetramethylbutyl)methylphosphino)methane (t-Oct-MiniPHOS), and (tert-butylmethylphosphino)(di-tert-butylphosphino)methane (trichickenfootphos) were prepared in good yields and enantiopure form.     

Criticality features in ULF magnetic fields prior to the 2011 Tohoku earthquake

The criticality of ULF (Ultra-low-frequency) magnetic variations is investigated for the 2011 March 11 Tohoku earthquake (EQ) by natural time analysis. For this attempt, some ULF parameters were considered: (1) F_h (horizontal magnetic field), (2) F_z (vertical magnetic field), and (3) D_h (inverse of horizontal magnetic field). The first two parameters refer to the ULF radiation, while the last parameter refers to another ULF effect of ionospheric signature. Nighttime (L.T. = 3 am ± 2 hours) data at Kakioka (KAK) were used, and the power of each quantity at a particular frequency band of 0.03–0.05 Hz was averaged for nighttime hours. The analysis results indicate that F_h fulfilled all criticality conditions on March 3–5, 2011, and that the additional parameter, D_h reached also a criticality on March 6 or 7. In conclusion, criticality has reached in the pre-EQ fracture region a few days to one week before the main shock of the Tohoku EQ.     

Electrocatalytic and photocatalytic water oxidation to dioxygen based on metal complexes

The construction of an artificial photosynthetic device requires detailed understanding of the catalytic aspects of photo- or photoelectro-driven water oxidation. This has been attracting much interest as one of the promising clean energy-providing systems for the future. This review mainly covers progress on electrocatalytic and photocatalytic systems for water oxidation in the last decade. It includes conventional iridium oxide colloid catalysts and the new electrodeposited cobalt-phosphate catalyst films for water oxidation.