This study investigates the impact of Sm and Mn co-doping on the structural, electronic, and magnetic properties of BiFeO3 ceramics (BFO, BSFO91, BSFMO91) synthesized via solid-state reaction. X-ray diffraction confirmed that co-doping suppressed the nonpolar Pbam phase and stabilized the rhombohedral R3c structure in BSFMO91. Distortion of FeO6 octahedra reduced the bandgap (1.58 eV) and Urbach energy (0.502 eV), indicating improved lattice order. Ferroelectric measurements showed enhanced remanent polarization (0.154 μC/cm2) and measurable recoverable energy storage. Electron spin resonance revealed strong spin–orbit interaction (g = 2.260), while magnetic studies indicated increased moment (0.025 μB/f.u.) and canting (0.289°). Temperature-dependent analysis confirmed weak ferromagnetism below 10 K. The findings highlight BSFMO91 as a promising multifunctional material for further exploration in magnetoelectric systems.
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