Phase Behavior and Crystal Structure of Perovskite-Type Rare Earth Complex Oxides

Several compounds of rare earth complex oxides containing manganese and titanium were synthesized in Ar, and their crystal structures were analyzed by powder X-ray diffraction data and Rietveld method. Structures of A0.67Ln0.33 Mn0.33Ti0.6703（A = Ca or Sr and Ln = rare earth） were found to have orthorhombic symmetry with the space group Pnrna, and their interatomic distances and bond angles were obtained. This space group was also derived from electron microscopic study. Electrical conductivity of Cao.67Ln0.33Mn0.33Ti0.6703 for several rare earth elements showed a semiconducting property with the activation energy of 0.4 eV. Some of these compounds of the strontium system show the antiferromagnetic properties below 10 K.

Stability of phases in (Ba, Gd)MnO_3 solid solution system

The existing phases in BaxGd1-xMnO3 solid solution system （0≤x≤ 1） were studied by analyzing the detailed crystal structure of each composition from the results of the Rietveld method using powder X-ray diffraction data. For a small substitution of Ba for Gd （0≤x〈0. 1）, the orthorhombic phase with a perovskite type structure （Pnma space group） was stably formed and this fact was supported by the electron diffraction data. There existed an intermediate phase of Ba0.33Gd0.67MnO3, which was characterized as the tetragonal phase with perovskite structure. The composition range of this phase was narrow and almost line compound. Between the regions of these phases, there existed two-phase region. There was also a two-phase region between the intermediate tetragonal phase and BaMnO3. Measurement of electrical conductivities of these orthorhombic solid solutions and tetragonal phases showed semiconducting behaviors for both phases and the existence of the phase transition at high temperature for the orthorhombic phase, The transition temperature decreased as the Ba content increased.

Structural Analysis of a New Phase of BaNdMnO_4

Single crystal of BaNdMnO4 with I4/mmm was synthesized by a floating zone method. A new phase of BaNdMnO4 was obtained by annealing the single crystal in a reducing atmosphere at 573 K for 10 d. The structural change was analyzed by four-circle X-ray diffractometry and transmission electron microscopy. The new phase has an orthorhombic unit cell (Fmmm) of a=0.5486(2) nm, b=0.5484(2) nm, and c=1.3059(2) nm.

Novel Phase Transition in BaPr_2Mn_2O_7

The rare earth manganite BaLn2Mn2O7(Ln = rare earth element) has a Sr3Ti2O7-type layered perovskite structure with double-block oxygen octahedra belonging to the Ruddlesden-Popper-type homologous series AO(ABO3)2. In Pr-manganite, a novel phase transition was first observed in situ at 1040 K by a thermal transmission electron microscope. At 1040 K, reflections began to split along the c-direction in the selected area diffraction pattern. This indicates that a new phase appears in the original phase matrix; the c length of the new phase is 1.5% longer than that of the original phase. After about 5 min, the original phase disappears. No change in the crystal symmetry (space group 14/mmm) is observed above 1040 K.