Barium oxynitridosilicates, Ba3Si6O12N2 and Ba3Si6O9N4, were obtained from a mixture of BaCN2 and SiO2 at 800 °C, which is several hundred degrees lower than the temperature required in solid state reactions using BaCO3, SiO2 and Si3N4. The low-temperature formation mechanism was investigated by thermogravimetry analysis in conjunction with gas chromatography and mass spectroscopy. The phase ratio between the oxynitridosilicates was controlled by tuning the reaction temperature, duration, and atmosphere. Almost single-phase Ba3Si6O12N2 was obtained by reaction at 800 °C for 15 h under a N2 atmosphere, but the product changed to Ba3Si6O9N4 after 50 h at 800 °C or by heating at 950 °C for 15 h. The photoluminescence properties of Eu-doped products obtained at 800 °C using a mixture of BaCN2 : Eu and SiO2 were investigated.
Perovskite-type oxynitride BaTaO2N has been attracting attention for its large dielectric constant, which is almost independent of the temperature by measurements on its ceramics. Its dielectric characteristics are attributed to polar nanoregions (PNRs) in the average cubic crystal structure. Polarization saturation to produce a butterfly-like piezoresponse force microscopy (PFM) signal was observed on BaTaO2N crystals in the present study. Reddish crystallites of BaTaO2N of up to 3.1 µm in size were grown using a BaCN2 flux. Grain growth proceeded through the formation of a Ruddlesden-Popper-type oxynitride from the reaction between BaTaO2N powder and molten BaCN2. Their electrical property was studied using PFM with special care because of the small size of the crystals. They were found to be much more highly insulating than its ceramics. Ferroelectricity with complete phase inversion was observed on an oxynitride perovskite crystal for the first time. A large coercivity of 50-60 V was observed in the measurement. Such ferroelectricity is ascribed to the PNRs induced by the polar linkages between cis-type TaO4N2 octahedra.
The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock-salt-like structures with different nitrogen contents, were synthesized by reacting MnO, Mn2 O3 , or MnO2 with molten NaNH2 at 240-280 °C. The anion contents and the Mn valence states were determined by combustion analysis, powder X-ray diffraction, and X-ray absorption near-edge structure analysis. An increase in the nitrogen content of rock-salt-based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1 m KOH solution. Nearly single-electron occupancy of the antibonding eg states and highly covalent Mn-N bonding thus enhance the ORR activity of nitrogen-rich manganese oxynitrides.
Efficient laser performance is demonstrated with Nd:GdVO4 crystals grown by the floating zone method. With a 2-at. % Nd-doped crystal a slope efficiency of 67% is achieved with pumping at 808 nm. We also find that pumping at 879 nm with a bandwidth of 1.8 nm is practical for laser diode pumping. With this pumping level the slope efficiency reaches 78%. High-quality Nd:GdVO4 crystals are successfully grown with as much as 15-at.% Nd concentration by the floating zone method without inclusions or macroscopic defects. Homogeneity and high reproducibility of crystal growth are confirmed.
