Magnetoelectric ordering of BiFeO3 from the perspective of crystal chemistry

In this paper we examine the role of crystal chemistry factors in creating conditions for formation of magnetoelectric ordering in BiFeO3. It is generally accepted that the main reason of the ferroelectric distortion in BiFeO3 is concerned with a stereochemical activity of the Bi lone pair. However, the lone pair is stereochemically active in the paraelectric orthorhombic beta-phase as well. We demonstrate that a crucial role in emerging of phase transitions of the metal-insulator, paraelectric-ferroelectric and magnetic disorder-order types belongs to the change of the degree of the lone pair stereochemical activity - its consecutive increase with the temperature decrease. Using the structural data, we calculated the sign and strength of magnetic couplings in BiFeO3 in the range from 945 C down to 25 C and found the couplings, which undergo the antiferromagnetic-ferromagnetic transition with the temperature decrease and give rise to the antiferromagnetic ordering and its delay in regard to temperature, as compared to the ferroelectric ordering. We discuss the reasons of emerging of the spatially modulated spin structure and its suppression by doping with La3+.Comment: 18 pages, 5 figures, 3 table

Structural and magnetic phases of Bi 1−x Ax FeO 3− δ (A=Sr, Pb) perovskites

The Bi1-xAxFeO3-δ (A = Sr, Pb) systems have been studied using the X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that around x ~ 0.06 the crystal symmetry changes from a rhombohedral (space group R3c) to pseudo-tetragonal. In the composition range 0.07 ≤ x ≤ 0.14 the phases with different symmetry of the unit cell coexist independent of synthesis conditions. The neutron powder diffraction shows that the iron ions have average oxidation state close to 3+. The magnetic structure for Bi0.5Sr0.5FeO3-δ is found to be G-type antiferromagnetic with magnetic moment of about 3.8 μB/Fe3+. The weak ferromagnetic state due to magnetoelectric interactions was revealed in the lightly doped rhombohedrally distorted compositions. No evidence for a spontaneous magnetization was observed for the pseudo-tetragonal phases. These compositions show irreversible nonlinear magnetization vs. field behavior apparently due to small local deviations from the collinearity of the magnetic moments.

Flexomagnetoelectric interaction in multiferroics

75.80.+q Magnetomechanical and magnetoelectric effects, magnetostriction, 75.50.Ee Antiferromagnetics,