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Structural evolution and magnetic behavior of Ba- and Mn-substituted BiFeO3: Impurity-driven artifacts and intrinsic limitations
Authors: M. Das, B. F. O. Costa, J. A. Paixão, V. A. Khomchenko
Ref.: J. Mater. Sci.: Mater. Electron. 36(33), 2129 (2025)
Abstract: This study focuses on the crystal structure and magnetic properties of Ba–Mn co-substituted BiFeO3 ceramics with nominal composition Bi0.85Ba0.15Fe1-xMnxO3 (0.1 ≤ x ≤ 0.5), synthesized via solid-state reaction. X-ray diffraction and piezoresponse force microscopy confirm a composition-driven structural transition from a polar rhombohedral (R3c) phase to a centrosymmetric tetragonal (I4/mcm) phase occurring at x ≈ 0.4. Mössbauer spectroscopy and scanning electron microscopy reveal that the weak ferromagnetic behavior observed at room temperature is governed by trace amounts of Mn-doped BaFe12O19 impurity phase – undetectable by conventional XRD. While low-temperature magnetization enhancement in Mn-rich samples likely arises from Mn3+–O–Mn4+ ferromagnetic interactions, these results underscore the difficulty of isolating intrinsic magnetic responses in Ba-substituted BiFeO3. Our findings emphasize the necessity of cross-validating structural and magnetic measurements to avoid misinterpretation of multiferroic behavior in systems prone to impurity formation.
