We have investigated the effects of La substitution on the oxygen stability, defects, leakage current and polarization properties in ferroelectric bismuth titanate (Bi4Ti3O12) by measuring the properties of single crystals and by ab initio electronic structure calculations. It is shown that electron holes arising from the incorporation of oxygen at oxygen vacancies act as detrimental carriers for leakage current at room temperature for the crystals of BiT and La-substituted BiT. La substitution is effective for reducing oxygen vacancies and thus electron holes, which is attributed to an excellent insulating property observed for La-substituted crystals. High-pressure oxygen annealing is demonstrated to improve the remanent polarization of La-substituted crystals.
Single crystals of bismuth titanate (BiT) and lanthanum-substituted BiT [Bi4−xLaxTi3O12 (BLT)] were grown by a self-flux method. BLT (x=0.85) showed a smaller remanent polarization (2Pr) along the a(b) axis of 41 μC/cm2 than 98 μC/cm2 for BiT, which mainly originates in its smaller ionic displacements along the a axis. Striped 90° domain walls as well as head-to-head and tail-to-tail 180° domain walls were observed for both crystals, and La substitution led to a marked decrease in the 90° domain width from 8.5 μm (BiT) to 2.5 μm for BLT (x=1.20). Piezoelectric-force microscope observations suggested that antiphase domain boundary (ADB) is present only for BLT and the ADB plays an important role in the formation of the 90° domain.
A highly efficient manganese‐promoted oxidative cyclization of unsaturated oximes to afford the corresponding 4,5‐dihydroisoxazoline alcohols was developed. A very low loading (generally 0.1–0.2 mol‐%) of Mn(acac)3 (acac = acetylacetonate) promoted the oxidative cyclization through the direct incorporation of molecular oxygen present in air (open flask) at room temperature.
A highly efficient manganese-catalysed hydroperoxidation of carbon–carbon double bonds of enynes as well as styrene derivatives using N-hydroxyphthalimide, N-hydroxybenzotriazole or N-hydroxysuccinimide was developed.
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