Perovskite-type oxynitrides ACa_0.2M_0.8O_2.6N_0.4 (A = Sr, Ba; M = Nb, Ta) were synthesized via the ammonolytic reaction between A₅M₄O₁₅ and CaCl₂, where the Ca²⁺ insertion and O²⁻/N³⁻ substitution occurred cooperatively. In terms of the average structure, SrCa_0.2Nb_0.8O_2.6N_0.4 and SrCa_0.2Ta_0.8O_2.6N_0.4 belong to the orthorhombic Pnma space group, and BaCa_0.2Nb_0.8O_2.6N_0.4 and BaCa_0.2Ta_0.8O_2.6N_0.4, the primitive cubic Pm $\overline{3}$ m group. The comparison between the experimental lattice volume and the summed ionic volume suggested that ACa_0.2M_0.8O_2.6N_0.4 have higher degrees of ionicity than AM'_0.2M_0.8O_3−xN_x (M′ = Li, Mg, Mn), but are more covalent than ANa_0.2M_0.8O_2.8N_0.2. Despite the significant mismatches of size and charge between Ca²⁺ and Nb⁵⁺ (or Ta⁵⁺), no cation ordering was detected on the octahedral site. On the other hand, the O/N distribution appeared to depend on the bonding geometry around the anion sites in a way N favors the straighter bonding connectivity of M−N−M. The band gap energies of ACa_0.2M_0.8O_2.6N_0.4 were estimated to be 1.9–2.25 eV depending on A and M. The band gaps and color properties of AMO₂N and AM'_0.2M_0.8O_3−xN_x (A = Sr, Ba; M = Nb, Ta; M′ = Li, Na, Mg, Ca, Mn) are compared. Thermogravimetry and differential scanning calorimetry were conducted in the air to assess the oxynitride stability. The electrical behaviors were studied by the equivalent circuit analysis of the impedance spectrum using compacted polycrystalline specimens, where BaCa_0.2Ta_0.8O_2.6N_0.4 was found to possess a bulk dielectric constant of 4550 along with an electrical conductivity of ≈10⁻⁶ S/cm at 27 °C. It remains, however, necessary to assess the extrinsic effects arising from the non-ideal sintering to interpret thoroughly the electrical property of BaCa_0.2Ta_0.8O_2.6N_0.4.

通过A ₅ M ₄ O ₁₅和CaCl ₂之间的氨解反应合成了钙钛矿型氮氧化物ACa _0.2 M _0.8 O _2.6 N _0.4 (A = Sr, Ba; M = Nb, Ta) ，其中Ca ²⁺插入和O ²⁻ /N ³⁻取代协同发生。从平均结构来看，SrCa _0.2 Nb _0.8 O _2.6 N _0.4和SrCa _0.2 Ta _0.8 O _2.6 N _0.4属于斜方Pnma空间群，BaCa _0.2 Nb _0.8 O _2.6 N _0.4和BaCa _0.2 Ta _0.8 O _2.6 N _0.4属于斜方晶系Pnma空间群。 , 原始三次方Pm $\stackrel{￣}{3}$ 米组。实验晶格体积与总离子体积之间的比较表明，ACa _0.2 M _0.8 O _2.6 N _{0.4比 AM' 0.2} M _0.8 O _{3− x} N _x (M' = Li, Mg, Mn)具有更高的离子度，但比 ANa _0.2 M _0.8 O _2.8 N _0.2共价更高。尽管Ca ²⁺和Nb ⁵⁺（或Ta ⁵⁺）之间的尺寸和电荷显着不匹配，但在八面体位点上没有检测到阳离子排序。另一方面，O/N 分布似乎取决于阴离子位点周围的键合几何形状，N 有利于 MN−M 的更直的键合连接。_{ACa 0.2} M _0.8 O _2.6 N _0.4的带隙能量估计为 1.9–2.25 eV，具体取决于 A 和 M。AMO ₂ N 和 AM' _0.2 M _0.8 O _{3− x} N _x ( A = Sr、Ba；M = Nb、Ta；M' = Li、Na、Mg、Ca、Mn）进行比较。在空气中进行热重分析和差示扫描量热分析以评估氮氧化物的稳定性。使用压实多晶样品通过阻抗谱的等效电路分析来研究电学行为，其中 BaCa _0.2 Ta _0.8 O _2.6 N _{0.4被发现具有 4550 的体介电常数以及 ≈10} ^-6 S/的电导率厘米，27°C。然而，仍然有必要评估非理想烧结所产生的外在影响，以彻底解释BaCa _0.2 Ta _0.8 O _2.6 N _0.4的电性能。