A novel quadruple perovskite oxide CeCu₃Co₄O₁₂ has been synthesized in high-pressure and high-temperature conditions of 12 GPa and 1273 K. Rietveld refinement of the synchrotron X-ray powder diffraction pattern reveals that this oxide crystallizes in a cubic quadruple perovskite structure with the 1:3-type ordering of Ce and Cu ions at the A-site. X-ray absorption spectroscopy analysis demonstrates the valence-state transitions in the ACu₃Co₄O₁₂ series (A = Ca, Y, Ce) from Ca²⁺Cu³⁺₃Co^3.25+₄O₁₂ to Y³⁺Cu³⁺₃Co³⁺₄O₁₂ to Ce⁴⁺Cu^2.67+₃Co³⁺₄O₁₂, where the electrons are doped in the order from B-site (Co^3.25+ → Co³⁺) to A′-site (Cu³⁺ → Cu^2.67+). This electron-doping sequence is in stark contrast to the typical B-site electron doping for simple ABO₃-type perovskite and quadruple perovskites CaCu₃B₄O₁₂ (B = V, Cr, Mn), further differing from the monotonical A′-site electron doping for Na_1–xLa_xMn₃Ti₄O₁₂ and A′- and B-site electron doping for AMn₃V₄O₁₂ (A = Na, Ca, La). The differences in the electron-doping sequences are interpreted by rigid-band models, proposing a wide variety of electronic states for the complex transition-metal oxides containing the multiple valence-variable ions.

中文翻译：

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四重钙钛矿氧化物ACu3Co4O12（A = Ca，Y，Ce）的顺序电子掺杂。

在高压和高温条件下（12 GPa和1273 K）合成了一种新型的四方钙钛矿氧化物CeCu ₃ Co ₄ O _12。同步加速器X射线粉末衍射图的Rietveld精炼显示该氧化物以立方四方结晶。钙钛矿结构，在A位点处Ce和Cu离子的1：3型排序。X射线吸收光谱分析表明，Ca ²⁺ Cu ³⁺ ₃ Co ^3.25+ ₄ O的A Cu ₃ Co ₄ O ₁₂系列（A = Ca，Y，Ce）的价态跃迁₁₂到Y ³⁺ Cu ³⁺ ₃ Co ³⁺ ₄ O ₁₂到Ce ⁴⁺ Cu ^2.67+ ₃ Co ³⁺ ₄ O ₁₂，其中电子从B位置开始依次掺杂（Co ^{3.25 +} →Co ³⁺）到A '位（Cu ³⁺ →Cu ^2.67+）。该电子掺杂序列与简单的AB O ₃型钙钛矿和四重钙钛矿CaCu ₃ B的典型B位置电子掺杂形成鲜明对比。₄ ø ₁₂（乙= V，铬，锰）中，从进一步monotonical不同甲'-site电子掺杂的Na _{1- X}的La _X的Mn ₃的Ti ₄ ö ₁₂和甲和- '乙-site电子掺杂为甲锰₃ V ₄ O ₁₂（A = Na，Ca，La）。刚性带模型可以解释电子掺杂序列中的差异，从而为包含多个化合价离子的复杂过渡金属氧化物提出了多种电子状态。