Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS

The dynamics of the local electronic and geometric structures of WO₃ following photoexcitation were studied by femtosecond time‐resolved X‐ray absorption fine structure (XAFS) spectroscopy using an X‐ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.     

Sequential Synthesis of Coordination Polymersomes

Novel organic–inorganic hybrid liposomes, so‐called coordination polymersomes (CPsomes), with artificial domains that exhibit strong lateral cohesion were prepared by a three‐step procedure that formed a coordinative interaction leading to a lipid bilayer. First, the lipophilic complex (dabco‐C₁₈)[Mn(N)(CN)₄(dabco‐C₁₈)] ( 1 ; dabco‐C₁₈⁺=1,4‐diazabicyclo[2,2,2]octane‐(CH₂)₁₇? CH₃ cation), was synthesized. 1 has a lipophilic alkyl tail part and a tetracyanometallate head group, which can be used for an expansion to two‐dimensional coordination networks. Second, 1 and 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine were mixed to prepare the liposomes. Finally, CPsomes were obtained by the addition of transition‐metal ions ( M ) to form unilamellar faceted liposomes with plain CP raft domains with Mn? CN? M linkages. The concentration of 1 influences the size of the CP raft domains and the shape of the CPsomes. The synthesis of coordination polymers in lipid bilayers is a novel approach for the construction of artificial architectures as raft domains, for example, in cell membranes.     

Synthesis of furan-substituted aza-BODIPYs having near-infrared emission

Development of near-infrared-emissive aza-boron dipyrromethene (aza-BODIPY) derivatives having furanyl groups is reported. From the optical measurements, it was clearly indicated that the emission bands were presented in the longer wavelength region than those of the conventional aza-BODIPYs. The emission bands with the peaks at 730 nm and 758 nm were observed from the bis- and tetra-substituted furanyl aza-BODIPYs with similar extents of emission efficiencies, respectively. According to the computer calculations, it was proposed that molecular planarity could be enhanced in the case of the furan groups. As a result, band-gap energy could be lowered comparing to those of the conventional benzene and thiophene-substituted aza-BODIPYs.     

Chromatographic behavior of small organic compounds in low‐temperature high‐performance liquid chromatography using liquid carbon dioxide as the mobile phase

Low‐temperature high‐performance liquid chromatography, in which a loop injector, column, and detection cell were refrigerated at –35ºC, using liquid carbon dioxide as the mobile phase was developed. Small organic compounds (polyaromatic hydrocarbons, alkylbenzenes, and quinones) were separated by low‐temperature high‐performance liquid chromatography at temperatures from –35 to –5ºC. The combination of liquid carbon dioxide mobile phase with an octadecyl‐silica (C₁₈) column provided reversed phase mode separation, and a bare silica‐gel column resulted in normal phase mode separation. In both the cases, nonlinear behavior at approximately –15ºC was found in the relationship between the temperature and the retention factors of the analytes (van't Hoff plots). In contrast to general trends in high‐performance liquid chromatography, the decrease in temperature enhanced the separation efficiency of both the columns.     

Metallic contaminant detection system using multi-channel high Tc SQUIDs

We have developed the magnetic metallic contaminant detectors using multiple high Tc SQUID gradiometers for industrial products. Finding ultra-small metallic contaminants is a big issue for manufacturers producing commercial products. The quality of industrial products such as lithium ion batteries can deteriorate by the inclusion of tiny metallic contaminants. When the contamination does occur, the manufacturer of the product suffers a great loss to recall the tainted products. Metallic particles with outer dimension less than 50 μm cannot be detected by a conventional X-ray imaging. Therefore a high sensitive detection system for small foreign matters is required. However, in most of the cases, the matrix of an active material coated sheet electrode is magnetized and the magnetic signal from the matrix is large enough to mask the signal from contaminants. Thus we have developed a detection system based on a SQUID gradiometer and a horizontal magnetization to date. For practical use, we should increase the detection width of the system by employing multiple sensors. We successfully realized an eight-channel high-Tc SQUID gradiometer system for inspection of sheet electrodes of a lithium ion battery with width of at least 60 to 70 mm. Eight planar SQUID gradiometers were mounted with a separation of 9.0 mm. As a result, small iron particles of less than 50 μm were successfully measured. This result suggests that the system is a promising tool for the detection of contaminants in a lithium ion battery.     

Evaluation of electron-hole recombination properties of titanium (IV) oxide particles with high photocatalytic activity

Electron-hole recombination in nano-sized titanium(IV) oxide (TiO₂) particles with various physical properties, which have been shown to be highly active photocatalysts, was evaluated by quantitative analysis of reduced titanium species (Ti³⁺), which might be formed at crystalline defective sites in TiO₂ particles through photo-irradiation in the presence of a hole scavenger under deaerated conditions. These highly active photocatalyst samples were synthesized by hydrothermal crystallization in organic media (HyCOM method) and post-calcination. The Ti³⁺ density decreased with increasing calcination temperature (T _c), and a linear correlation was observed between the Ti³⁺ density and rate constant for electron-hole recombination evaluated by femtosecond pump-probe diffuse reflection spectroscopy. Reaction rate (R _Ag) and the amount of silver ions (Ag⁺) adsorbed on TiO₂ particles ([Ag⁺]_ads) were measured for photocatalytic silver metal deposition along with oxygen formation from an aqueous Ag⁺ solution under deaerated conditions, and the slope of the R _Ag versus [Ag⁺]_ads plot was determined. Kinetic investigation of this reaction showed that the reciprocal of the slope was approximately related to the ratio of the rates for electron-hole recombination and electron trapping (k _r/k _e ratio). The k _r/k _e ratio decreased as T _c increased, and the logarithm of the k _r/k _e ratio was linearly related with Ti³⁺ density. These two parameters were used as a measure for the recombination properties of TiO₂ photocatalysts with various physical properties.     

Signal Formation of Image-Edge Motion Based on Biological Retinal Networks and Implementation into an Analog Metal-Oxide-Silicon Circuit

A simplified model was proposed for the formation of edge signals and generation of motion signals of a target based on the information processing mechanisms of outer and inner retinas of a vertebrate. Analog metal-oxide-silicon (MOS) integrated circuits were designed based on the model. Simulation program with integrated circuit emphasis (SPICE) simulation results showed the performance of local adaptation over a wide dynamic range in the outer retinal circuit and generation of the velocity signal of a moving edge in the inner retinal circuit. Preliminary experimental results showed local adaptation in a given input range in the outer retinal circuit and the generation of motion pulsed signals in the inner retinal circuit.     

Step bunching behaviour on the {0 0 0 1} surface of hexagonal SiC

Surface topography of the {0 0 0 1} facet plane of as-grown 6H- and 4H-SiC crystals was studied ex situ by Nomarski optical microscopy (NOM) and atomic force microscopy (AFM). The surface polarity and the polytype of grown crystals largely affect the growth surface morphology of SiC{0 0 0 1} via differences in several thermodynamic and kinetic parameters. NOM observations revealed giant steps of a few micrometers in height on the {0 0 0 1} growth facet, and it was found that a morphological transition of the growth facet occurred when the growth conditions were changed. AFM imaging of the stepped structure of SiC{0 0 0 1} detected steps of height equal to the unit c-lattice parameter (c=1.512 nm for 6H-SiC and 1.005 nm for 4H-SiC). They are fairly straight and very regularly arranged, giving rise to equidistant step trains. Upon nitrogen doping, these regular step trains on the 6H-SiC(0 0 0  )C and 4H-SiC(0 0 0  )C surfaces became unstable: the equidistant step trains were transformed into meandering macrosteps of height greater than 10 nm. In this paper, we discuss the mechanism of macrostep formation (step bunching) on the SiC{0 0 0 1} surfaces through the consideration of the interplay between step energetics (repulsive step interaction) and kinetics (asymmetric step kinetics) on the growing crystal surface and elucidate how they affect the growth surface morphology of the SiC{0 0 0 1} facet.     

Quantitative Auger analysis of ion-implanted boron and arsenic in polycrystalline silicon

Quantitative analysis of boron and arsenic in silicon has been made by Auger electron spectroscopy with the in-situ ion milling technique. Ion-implanted boron and arsenic in polycrystalline silicon was used as standard samples. The experimental results indicate that the semi-empirical formalism for quantitative Auger analysis is valid for impurity concentrations less than a few percent. Excellent linear relationship has been obtained between the implanted dose and the normalized Auger signal intensity within ±10% for boron and ±20% for arsenic in silicon.