Magnetic structure and properties of Ca, Mn-doped bismuth ferrites near the polar/nonpolar phase boundary

Abstract

Neutron diffraction and magnetization measurements of the Bi0.85Ca0.15Fe1-xMnxO3+δ (x = 0.4, 0.5) compounds have been performed at room and low temperatures to disclose the effect of the mixed-valence Mn substitution on the magnetic structure and properties of the Ca-doped bismuth ferrites near the polar/nonpolar phase boundary. It has been confirmed that the Mn substitution results in the filling of anion vacancies produced by the aliovalent replacement of Bi3+ by Ca2+. The Bi0.85Ca0.15Fe0.6Mn0.4O3+δ compound has the acentric structure specific to the pure BiFeO3 (space group R3c) and displays a G-type antiferromagnetic order at room temperature (m300K = 1.35(2) μB). The magnetic moments localized on the Fe/Mn ions are directed along the polar axis. The spin-reorientation transition from the c to a axis takes place with decreasing temperature. An increase in the Mn concentration gives rise to the polar → nonpolar (R3c → Pnma) structural phase transformation. The nonpolar (x = 0.5) compound has a G-type antiferromagnet structure (TN = 210 K) with spins aligned along the orthorhombic b axis. The low-temperature magnetic moments (m5K = 2.67(2) μB and m5K = 1.80(3) μB for the samples with x = 0.4 and x = 0.5, respectively) are considerably smaller than those predicted for complete spin ordering of the interacting ions of Fe3+, Mn3+ and Mn4+ (>4 μB). While the neutron diffraction measurements reveal no contribution associated with a long-range ferromagnetic order at T = 5 K, a significant increase in the magnetization of the samples, suggesting the formation of a glassy phase, is observed with decreasing temperature.