Electric relaxation and Mn3+/Mn4+ charge transfer in Fe-doped Bi12MnO20–BiMn2O5 structural self-composite

Fe-doped Bi12MnO20–BiMn2O5 ceramics was sintered at 1130 K for 6 h in ambient air. Two centro-symmetric phases formed thermodynamically stable self-composite material that was deduced from X-ray pattern analysis. The lattice parameters were a = 10.147(8) Å—for the cubic I23 Bi12MnO20 phase; and a = 7.545(4) Å, b = 8.538(1) Å, c = 5.758(3) Å—for the orthorhombic Pbam BiMn2O5 phase. The 57Fe Mössbauer spectrum, recorded at room temperature, has shown pure electronic quadrupolar split. The major doublets reflected the occurrence of Fe3+ ions distributed in two sites, i.e., octahedral Fe4+O6 and square pyramidal Fe3+O5, with preferential occupation of the pyramidal sites, that was consistent with the Pbam phase symmetry. The third doublet resulted from the presence of iron Fe3+ in tetrahedral Fe3+O4 coordination and corresponded to a small admixture of the I23 phase. The DC resistivity ρ DC(T) dependence on temperature has shown thermally activated features, and the value of E a,DC varied in the range of 0.22–0.37 eV. The electric impedance was measured in the f = 20 Hz–1 MHz and 100–690 K range. Two electrical relaxations were determined using the electric modulus formalism M″(T). Low-temperature relaxation has shown the temperature-dependent activation energy E A,1 = 0.14–0.20 eV and characteristic time values of τ 01 = 10−10–10−12 s in 100–200 K range. It was attributed to the charge transfer between Mn4+/Mn3+ sites. The other relaxation occurred in the 170–220 K range, and it exhibited the following values: τ 02 = 10−11 s, and E A,2 = 0.27 eV. A disorder-related VRH polaron model was proposed for ρ DC(T) and for electric relaxation processes.