Hosono Akira, Masubuchi Yuji, Endo Takashi, Kikkawa Shinichi
Graduate School of Chemical Science and Engineering, Hokkaido University, N13 W8, Kita-ku, Sapporo 060-8628, Japan.
Faculty of Engineering, Hokkaido University, N13 W8, Kita-ku, Sapporo 060-8628, Japan.
Dalton Trans. 2017 Dec 12;46(48):16837-16844. doi: 10.1039/c7dt03765a.
Solid phase sintering of dielectric oxynitride perovskites above 1000 °C is accompanied by their decomposition. Post-ammonolysis is required to recover their stoichiometric nitrogen content and dielectric properties. In the present work, the oxynitride perovskite SrTaON was sintered with a BaCN flux at approximately 900 °C avoiding its thermal decomposition. The resulting solid product with a relative density of 68.9% showed relative dielectric constants in the range from 68 to 90 with loss values less than 0.11, without the post-ammonolysis. The interior of the solids contained rectangular SrBaTaON crystals for which 0.04 ≤ x ≤ 0.23 reflecting their euhedral form. These crystals were grown in molten BaCN from 20 to 100 times larger than the original SrTaON particles and had a maximum grain size of 3.7 μm. The SrBaTaON precipitated on the surfaces of the residual SrTaON crystals that had partially dissolved in the BaCN flux. A compositional gradient from barium-rich to strontium-rich was observed in a single crystal of the product on going from the exterior to the interior. This is the first-ever report of the preliminary liquid phase sintering and crystal growth of a dielectric oxynitride perovskite using a molten metal cyanamide.
介电氮氧化物钙钛矿在1000℃以上进行固相烧结时会伴随分解。需要进行氨解后处理以恢复其化学计量的氮含量和介电性能。在本工作中,氮氧化物钙钛矿SrTaON在约900℃下与BaCN助熔剂一起烧结,避免了其热分解。所得相对密度为68.9%的固体产物在不进行氨解后处理的情况下,相对介电常数在68至90范围内,损耗值小于0.11。固体内部含有矩形的SrBaTaON晶体,其中0.04≤x≤0.23,反映了它们的自形形态。这些晶体在熔融的BaCN中生长,比原始的SrTaON颗粒大20至100倍,最大晶粒尺寸为3.7μm。SrBaTaON沉淀在部分溶解于BaCN助熔剂的残余SrTaON晶体表面。在产物的单晶中,从外部到内部观察到从富钡到富锶的成分梯度。这是首次报道使用熔融金属氰胺对介电氮氧化物钙钛矿进行初步液相烧结和晶体生长。