Role of Ti 3d carriers in mediating the ferromagnetism of Co∶TiO2 anatase thin films

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co∶TiO(2) anatase films using soft- and hard-x-ray photoemission spectroscopy with probe sensitivities of ～1 and ～10 nm, respectively. We obtain direct evidence of metallic Ti(3+) states in the bulk, which get suppressed to give a surface semiconductor, thus indicating the difference in electronic structure between surface and bulk. X-ray absorption and resonant photoemission spectroscopy reveal Ti(3+) electrons at the Fermi level (E(F)) and high-spin Co(2+) electrons occurring away from E(F). The results show the importance of the charge neutrality condition: Co(2+)+V(O)(2-)+2Ti(4+)?Co(2+)+2Ti(3+) (V(O) is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.     

The phase diagram for coexisting d-wave superconductivity and charge-density waves: cuprates and beyond

Phase diagrams of d-wave superconductivity characterized by an order parameter Δ coexisting with charge-density waves (CDWs) characterized by an order parameter Σ were constructed for the two-dimensional Fermi surface (FS) appropriate to, e.g., cuprates. CDWs were considered as an origin of the pseudogap appearing at antinodal FS sections of the d(x2-y2) superconductor. Two types of the Σ-reentrance were found: with the temperature, T, and with the opening of the CDW sector, 2α. The angular plots in the momentum space for the resulting gap profile over the FS ('gap roses') were obtained. The gap patterns are rather involved, giving insight into the difficulties of the interpretation of photoemission spectra. It was shown that the Σ-Δ coexistence region exists even for the complete dielectric gapping due to the distinction between the superconducting and CDW order parameter symmetries. The checkerboard and unidirectional CDW configurations were examined, and both the phase diagrams and the behavior with T and α of the order parameters were found to differ. A more general case with a non-zero mismatch angle β between the superconducting lobes and the CDW sectors was analyzed, the case β = π/4 corresponding to the d(xy) symmetry of the superconducting order parameter. The phase diagrams were found to be sensitive to β-variations, showing that internal strains and external pressure can drastically affect the behavior of Σ(T) and Δ(T).     

9,9′‐spirobifluorene‐containing polycarbonates: Transparent polymers with high refractive index and low birefringence

Syntheses of 2,2′‐bisalcoholic group‐substituted 9,9′‐spirobifluorene monomers 2 were performed by the reaction of 2,2′‐dihydroxy‐9,9′‐spirobifluorene 2a with haloalcohols. Polycarbonates consisting of 9,9′‐spirobifluorene skeleton in the main chain (PC 4 ) were synthesized by the polycondensation of 2,2′‐bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. PC 4 showed good thermal stability: the 5% weight loss temperature was over 330 °C under both nitrogen and air atmospheres. The glass transition temperature was in a range of 16–269 °C estimated by differential scanning calorimetry, depending on the flexibility of the alkylene or oxyethylene chains of 2 . PC 4 showed high solubility toward ordinary organic solvents such as CHCl₃, benzene, and THF, making possible the preparation of the flexible thin films. Very high refractive index in a range of 1.62–1.66 at 589 nm was observed although PC 4 consists only of C, H, and O atoms, whereas very low degree of birefringence was confirmed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3658–3667, 2010     

Luminescent properties of phenylenediamine derivatives depending on the redox states

Phenylenediamines bearing the ethoxycarbonyl groups were synthesized to modulate luminescent properties. Switching of the luminescent properties was achieved by redox change between the phenylenediamine and quinonediimine derivatives.     

Closed orbits in homology classes

Dedicated to Pr. Akihiko Morimoto for his 60th birthday     

Redox-switchable π-conjugated systems bearing terminal ruthenium(II) complexes

p-Phenylenediamine bearing terminal bipyridyl moieties was synthesized by palladium-catalyzed amination. The corresponding ruthenium(II) complex was formed and characterized, providing a redox-switchable photoinduced electron-transfer system.     

Development of a micromachined piezoelectric microphone for aeroacoustics applications

This paper describes the design, fabrication, and characterization of a bulk-micromachined piezoelectric microphone for aeroacoustic applications. Microphone design was accomplished through a combination of piezoelectric composite plate theory and lumped element modeling. The device consists of a 1.80-mm-diam, 3-microm-thick, silicon diaphragm with a 267-nm-thick ring of piezoelectric material placed near the boundary of the diaphragm to maximize sensitivity. The microphone was fabricated by combining a sol-gel lead zirconate-titanate deposition process on a silicon-on-insulator wafer with deep-reactive ion etching for the diaphragm release. Experimental characterization indicates a sensitivity of 1.66 microVPa, dynamic range greater than six orders of magnitude (35.7-169 dB, re 20 microPa), a capacitance of 10.8 nF, and a resonant frequency of 59.0 kHz.     

Shape and structure recovery of an LCP droplet under a large step strain: observation and stress calculation

Shape recovery of a droplet of liquid crystalline polymer (LCP) hydroxypropylcellulose in a matrix of poly(dimethyl siloxane) subjected to a step shear strain has been studied via optical microscopy. Just after application of a large strain, the LCP droplet shape is flat ellipsoid, and then the droplet takes cylindrical shape and band texture perpendicular to the flow direction appears. The band texture fades away before emergence of poly-domain structure. In the final process with the shape of spheroid, poly-domain structure recovers very slowly. Except for the final process, the shape change is identical with that of isotropic droplet at strains smaller than 3, when the LCP viscosity in Region II is taken as an equivalent viscosity for normalization. For a 20:80 blend, the excess relaxation modulus is calculated based on the Doi-Ohta theory, taking account of the distribution of droplet size and compared with experimental modulus data.