A Sequential Electron Doping for Quadruple Perovskite Oxides ACu₃Co₄O₁₂ (A = Ca, Y, Ce)

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-LaMn₃Ti₄O₁₂ 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.