Structural, Raman, and dielectric studies on multiferroic Mn-doped Bi 1-xLax FeO 3 ceramics

Multiferroic Bi1-xLaxFeO3 [BLFO (x)] ceramics with x = 0.10-0.50 and Mn-doped BLFO (x = 0.30) ceramics with different doping contents (0.1-1.0 mol%) were prepared by solid-state reaction method. They were crystallized in a perovskite phase with rhombohedral symmetry. In the BLFO (x) system, a composition (x)-driven structural transformation (R3c→C222) was observed at x = 0.30. The formation of Bi2Fe 4O9 impure phase was effectively suppressed with increasing the x value, and the rhombohedral distortion in the BLFO ceramics was decreased, leading to some Raman active modes disappeared. A significant red frequency shift (~13 cm-1) of the Raman mode of 232 cm-1 in the BLFO ceramics was observed, which strongly perceived a significant destabilization in the octahedral oxygen chains, and in turn affected the local FeO6 octahedral environment. In the Mn-doped BLFO (x = 0.30) ceramics, the intensity of the Raman mode near 628 cm-1 was increased with increasing the Mn-doping content, which was resulted from an enhanced local Jahn-Teller distortions of the (Mn,Fe)O6 octahedra. Electron microscopy images revealed some changes in the ceramic grain sizes and their morphologies in the Mn-doped samples at different contents. Wedge-shaped 71° ferroelectric domains with domain walls lying on the {110} planes were observed in the BLFO (x = 0.30) ceramics, whereas in the 1.0 mol% Mn-doped BLFO (x = 0.30) samples, 71° ferroelectric domains exhibited a parallel band-shaped morphology with average domain width of 95 nm. Dielectric studies revealed that high dielectric loss of the BLFO (x = 0.30) ceramics was drastically reduced from 0.8 to 0.01 (measured @ 104 Hz) via 1.0 mol% Mn-doping. The underlying mechanisms can be understood by a charge disproportion between the Mn4+ and Fe2+ in the Mn-doped samples, where a reaction of Mn4+ + Fe2+→Mn3+ + Fe3+ is taken place, resulting in the reduction in the oxygen vacancies and a suppression of the electron hopping from Fe3+ to Fe2+ ions effectively. © 2014 The American Ceramic Society.