Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Quantum dynamics study on the product branching for the C(3P) + C2H2 reaction: cyclic-C3H versus linear-C3H

Reduced-dimensionality quantum reactive scattering calculations for the C(3P) + C2H2 reaction have been carried out in order to understand the product branching dynamics of cyclic-C3H + H and linear-C3H + H. Our model treats only two degrees of freedom but can explicitly describe both of the C3H isomer product channels. The lowest triplet potential energy surface has been obtained by the hybrid density-functional method at the B3LYP/6-31G(d,p) level of theory. The calculated reaction probabilities were found to be dominated by resonance consistent with the complex-formation potential, and the results show that cyclic-C3H is preferentially formed via the cyclic-C3H2 intermediate produced by insertion of C(3P) into the CC bond. We have found that the isomerization from the cyclic-C3H2 to linear-C3H2 intermediate is suppressed by a barrier separating potential wells corresponding to these two intermediates. It has also been found that the energy dependence of the calculated total reaction cross section is in good agreement with the result of crossed molecular beam experiments.     

The concentration profiles of the recoil implanted oxygen in Si after ion implantations into SiO2-Si substrates

Abstract

The annealing of bare thermal oxide on silicon at 400–500°C in a hydrogen bearing gas results in a reduced density of states N_ss at the substrate silicon/oxide interface. Treatments of this type have played a role in MOS processing schedules for several years. However, a similar approach applied to large areas (cm²) of poly-silicon coated oxide appears to be less effective in reducing N_ss. This may be due to the polysilicon acting as a partially impermeable barrier which tends to starve the substrate/oxide interface of hydrogen.

In the present work hydrogenation of 2-inch diameter, polysilicon coated wafers has been accomplished by hydrogen ion implantation. H2⁺ ions of 135 kV energy were implanted (to a dose of 10¹⁵ cm^?2) through a 7000 Å polysilicon coating into an underlying 1400 Å SiO₂ layer. The polysilicon was removed after 30-min anneals carried out in pure N₂ at 300, 400 or 500°C. Aluminium dots, 1 mm in diameter were then deposited on to the oxide and high frequency (1 MHz) and quasistatic C-V curves recorded for determinations of Nss. Control anneals on unimplanted material were carried out in pure N₂ and N₂-H₂ ambients. Control samples annealed in pure N₂ with their polysilicon coating intact had mid-gap N_ss values of not less than 4 × 10¹⁰ cm^?2 eV^?1. The corresponding value after N₂-H₂ anneals on polysilicon-free wafers was 3 × 10¹⁰. H₂ ⁺ implanted samples annealed in pure N₂ with their polysilicon intact had mid-gap N_ss values of 1 × 10¹⁰ cm^?2 eV^?1.

The effectiveness of ion beam hydrogenation may depend upon confinement of the associated displacement damage to the polysilicon. This allows the implanted hydrogen to be activated within the SiO₂ at temperatures similar to those employed for normal hydrogeneous gas annealing of the substrate silicon/oxide interface.     

Electric-field control of electron–hole wave functions in a wide quantum well

The electric field dependence of the electron/hole wave function and the radiation energy of an exciton in a Be-δ-doped 80 nm quantum well (QW) is studied experimentally and compared it with variational calculation. The photoluminescence (PL) spectra show Stark shifts depending on the gate electric field and PL intensity of the exciton of the first excited state has a dip in the electric-field dependence which reflects the node of the electron wave function.     

Parametric control of a superconducting flux qubit

Parametric control of a superconducting flux qubit has been achieved by using two-frequency microwave pulses. We have observed Rabi oscillations stemming from parametric transitions between the qubit states when the sum of the two microwave frequencies or the difference between them matches the qubit Larmor frequency. We have also observed multiphoton Rabi oscillations corresponding to one- to four-photon resonances by applying single-frequency microwave pulses. The parametric control demonstrated in this work widens the frequency range of microwaves for controlling the qubit and offers a high quality testing ground for exploring nonlinear quantum phenomena of macroscopically distinct states.     

Theoretical studies on Josephson π states

The Josephson effect under particle-number restriction is investigated based on the Feynman two-state model. The existence of new dynamical states of the Josephson phase inherent in such a restricted situation is shown. The new state describes a number of features recently observed in a superfluid³He weak-link system. Quantum decay from Josephsonπ states is also investigated. Since the π state has two different decay paths, they can interfere during the decay processes by quantum tunneling due to a topological phase originating from total particle-number restriction, and result in a parity effect for tunneling.     

Mechanism of silver(I)-catalyzed Mukaiyama aldol reaction: active species in solution in AgPF6-(S)-BINAP versus AgOAc-(S)-BINAP systems

Silver(I)-diphosphine complex is an effective catalyst for Mukaiyama Aldol reaction in polar solvents. AgPF₆-(S)-BINAP cationic chiral complex indicated a good activity and could afford fairly high enantioselectivity in the reaction of aromatic aldehydes and silyl enol ethers. On the other hand, AgOAc-(S)-BINAP system afforded the aldol product of the absolute configuration opposite to that by AgPF₆-(S)-BINAP and very high catalytic activity was shown. The structure and equilibrium state of Ag(I)-BINAP complexes in solution were examined to understand the reaction mechanism. In AgPF₆ system [Ag((S)-BINAP)₂]PF₆ (1a), [Ag((S)-BINAP)]PF₆ (1b), [Ag₂((S)-BINAP)](PF₆)₂ (1c) and AgPF₆ are present in solution. The active species of the aldol reaction in DMF is [Ag((S)-BINAP)]PF₆ (1b), which exists as a minor species in solution. For this cationic Ag(I) catalyst, cyclic transition state containing substrate and silyl enol ether is assumed. In AgOAc-(S)-BINAP system, active species is also monomeric AgOAc((S)-BINAP) (2b) species which exists as a major component in solution and strong interaction was observed with a silyl enol ether. The reaction by AgOAc-(S)-BINAP catalyst is concluded to proceed as follows: nucleophile forms a complex with AgOAc-(S)-BINAP species and is activated. This complex attacks aldehydes to afford aldol adduct via acyclic transition state.     

Agariblazeispirols A and B, an unprecedented skeleton from the cultured mycelia of the fungus, Agaricus blazei

Agariblazeispirols A and B, which have a unique steroidal skeleton, have been isolated from the cultured mycelia of Agaricus blazei (Agaricaceae). The absolute structure of Agariblazeispirol A was established to be (20S,22R,23R,24S)-13β,22:22,25-diepoxy-5-methoxy-14β-methyl-18-nor-des-A-ergosta-5,7,9,11-tetraen-23-ol by extensive 1D and 2D NMR spectral data, and X-ray analysis. The structure of Agariblazeispirol B was elucidated to be a stereoisomer of agariblazeispirol A at its carbon 22, (20S,22S,23R,24S)-13β,22:22,25-diepoxy-5-methoxy-14β-methyl-18-nor-des-A-ergosta-5,7,9,11-tetraen-23-ol by comparison of extensive 1D and 2D NMR spectral data with those of agariblazeispirol A. Both compounds showed a moderate circumvention of drug resistance on mouse leukemia P388/VCR cells.     

Mechanical relaxation of single crystal mats of polyethylene in a crystalline dispersion region

Stress-relaxation measurements have been conducted over the temperature range 15°–105°C on mats of single crystals of two linear polyethylene fractions. The single crystals were grown isothermally at several different temperatures. The relaxation modulus was observed to be strain dependent, indicating that the single crystal mats exhibited nonlinearity.

In spite of this appearance of nonlinearity, it was found possible, when the relaxation modulus was extrapolated to zero strain by an appropriate method, to obtain correct relaxation spectra for the mats of single crystals prepared by isothermal crystallization. This spectrum was then used to calculate the dynamic viscoelastic functions and, for the unannealed sample crystallized at 80°C, good agreement was found between experimental results and calculated ones. Two annealed samples showed multiple absorptions and, under these circumstances, strict application of the method of reduced variables for time and temperature was impractical.

The effect of molecular weight on the intensity of the relaxation spectrum was investigated. It was found that the single crystal with the higher molecular weight showed an increased spectrum intensity.

Observations were also made of the effect of increased lamellar thickness on both the relaxation spectra and the dynamic complex moduli and the results obtained on the fractions studied were compared with prior studies in whole polymer.