Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn2Mn2O7(Ln=rare earth) with the layered perovskite type and Ln2(Mn,M)O7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn2Mn2O7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEuzMn207 at least five phases have been identified from the re-sults of X-ray diffraction analysis with the space group P42/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal 14/mmm phase. In the pyrochlore-related type compounds, LnzMn2-xMxO7(M=Ta,Nb,W etc),there also appear several phases with different crystal structures. With regard to every rare earth, Ln2MnTaO7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3121 space group). On the other hand Ln2Mn2/3Nb4/307 phase has monoclinic (C2/c space group)and zireonolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn2Mn2O7 (Ln=rare earth) with the layered perovskite type and Ln2(Mn, M)O7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn2Mn2O7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu2Mn2O7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P42/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln2Mn2-xMxO7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln2MnTaO7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3121 space group). On the other hand Ln2Mn2/3Nb4/3O7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.