Three-dimensional electronic structure in highly doped NaxCoO2 studied by angle-resolved photoemission spectroscopy

We have investigated three-dimensional electronic structure for Na_xCoO₂ (x=0.77 and 0.65) by high-resolution angle-resolved photoemission spectroscopy to study the origin of antiferromagnetic (AF) transition of highly doped Na_xCoO₂(x>0.75). The a_1g large hole-like Fermi surface (FS) in x=0.77 shows distinct three-dimensionality along the k_z direction, and a three-dimensional small electron pocket appears around Γ point, indicating strong inter-layer electronic correlation. On the other hand, x=0.65 sample does not show three-dimensional behavior. This result indicates that transition of FS as a function of band filling is closely related to the occurrence of the magnetic transition in highly doped Na_xCoO₂.     

Fabrication of a freestanding GaN layer by direct growth on a ZnO template using hydride vapor phase epitaxy

A new hydride vapor phase epitaxy (HVPE)-based approach for the fabrication of freestanding GaN (FS-GaN) substrates was investigated. For the direct formation of low-temperature GaN (LT-GaN) layers, the growth parameters were optimized: the polarity of ZnO, the growth temperature, and the V/III ratio. The FS-GaN layer was achieved by gas etching in an HVPE reactor. A fingerprint of Zn out-diffusion was detected in the photoluminescence measurements, especially for the thin (80 μm) FS-GaN film; however, a thicker film (400 μm) was effectively reduced by optimization of GaN growth.     

Synthesis and spectroscopic study of diphenylamino-substituted phenylene-(poly)ethynylenes: remarkable effect of acetylenic conjugation modes

A series of diphenylamino-substituted phenylene-(poly)ethynylenes were successfully synthesized by a combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. When UV-light was irradiated, the amino-substituted phenylene-(poly)ethynylene emitted strong luminescence. The emission underwent a large bathochromic shift in polar solvent because of stabilization of their charge-separated excited states. Analyses of fluorescence life times of aminoacetylenes revealed that radiationless process was suppressed in the polar solvent CH₂Cl₂, resulting in high quantum yields.     

X-ray absorption spectral analyses by theoretical calculations for TiO2 and Ni-doped TiO2 thin films on glass plates.

Ni L- and Ti L-edge as well as Ti K-edge X-ray absorption experiments for TiO2 thin films and Ni-doped TiO2 thin films coated on glass plates were performed using synchrotron radiation to investigate the structures around Ni and Ti ions in the films. The obtained spectra were compared with the results of theoretical calculations. It has consequently been found that the spectral features were affected by a change in the oxidizing form of Ni ions due to hydrogen reduction, by the charge variation and/or slight orbital splitting of Ti ions, and by the magnitude of the interaction between the center Ti ion and neighboring Ti ions.     

Orientationally disordered solid monolayers of tetramethylsilane on graphite and a bilayer nature of the 2-D fluid

A calorimetric investigation of the monolayers (MLs) of tetramethylsilane (TMS) adsorbed on graphite demonstrates two remarkable features: (i) occurrence of an orientational order–disorder phase transition in the 2-D solid (at 107 K at the coverage θ<1 and at 138 K at 1<θ<2) accompanied by a large entropy change (ranging from Rln8 to Rln3) depending on the coverage, and (ii) possible formation of a fluid bilayer around 220 K, above the 2-D critical temperature. A high-resolution incoherent neutron scattering experiment reveals a considerable motional disorder in the disordered 2-D solid.     

The effect of UV irradiation on the reduction of Au(III) ions adsorbed on manganese dioxide.

The effect of UV (ultraviolet) irradiation on the adsorption of Au(III) ions on manganese dioxide and their reduction to Au(0) (gold with 0 valence state) was investigated using XPS (X-ray photoelectron spectroscopy) and 197Au M?ssbauer spectroscopy. The UV irradiation accelerated the adsorption and the reduction. From the fact that the proportion of Au(0) estimated from Au 4f XPS spectra for surface analysis was significantly smaller than that from 197Au M?ssbauer spectra for bulk analysis, we deduced that Au(0) was interpenetrated to the inside of manganese dioxide (into deeper places than about 30 A) where XPS is impossible to detect. The content of surface hydroxyl groups on manganese dioxide also increased due to the UV irradiation. The relationship between the charge in the content of hydroxyl groups and the interpenetration of Au(0) is discussed.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Locally conformally Hermitian-flat manifolds

We introduce the notion of a locally conformally Hermitian-flat manifold and derive a necessary and sufficient condition for a Hermitian manifold to be locally conformally Hermitian-flat. In addition, we construct a family of examples.