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2004 | 105 | 1-2 | 173-182
Article title

Phase and Structural Study of Self-Doped La_{1-x-y}Ca_xØ_yMnO_{3+δ}

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To understand the combined effect of divalent ion and A-site vacancy (Ø) self-doping, beyond the binary La_{1-x}MnO_3 system, polycrystalline La_{1-x-y}Ca_xØ_yMnO_{3+δ} samples were studied. Samples with Ca substitution and excess Mn in the range x<0.33 and y<0.45, respectively, were prepared by standard solid-state reactions. Structural and phase analysis of the samples were done by X-ray diffraction and transmission electron microscopy. The manganite structure in this composition range includes rhombic and orthorhombic phases. Most samples contain the hausmanite phase (Mn_3O_4) coexisting with the manganite phase. A small amount of perovskite related AMn_7O_{12} (A=La,Ca) structure near the hausmanite-manganite boundary is also found in samples treated in oxygen atmosphere. The calculated vacancy content accommodated in the manganite phase can be higher than 1/8, the reported limit for La_{1-x}MnO_3, which is confirmed in our x=0 sample. For the compositions studied, a ferromagnetic metallic behavior below T_C is found, confirming the stability of the Mn sublattice, and near the optimum stoichiometric ((x=0. 33, y=0) system, a net A-site vacancy content (up to y=0.2) does not degrade the magnetic and electric properties.
Physical description
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