Novel multiferroic (Pb1 - 3x/2Ndx)(Ti0.98 - yFeyMn0.02)O3 ceramics with coexisting ferroelectricity and ferromagnetism at ambient temperature

We report the evolution of structural, dielectric, ferroelectric and ferromagnetic properties in novel (Pb1 - 3x/2Ndx) (Ti0.98 - yFeyMn0.02)O-3 perovskite ceramics (x = 0.08, 0 < y < 0.05). We found room-temperature ferroelectric polarization and ferromagnetism for higher amount of iron ions(y >= 0.04). The paraelectric-ferroelectric phase transition occurred between 650 and 670 K for 0 <= y <= 0.05. Ferromagnetic hysteresis was measured at different temperatures on samples with y >= 0.04. Detailed structural analysis evidenced the variation of unit cell parameters with y increasing, confirming the substitution of the iron element in the lattice. Fe-57 Mtissbauer spectroscopy evidenced that iron ions occupy Ti positions in the perovskite lattice, with the oxidation state Fe3+ and two coordination types. X-ray photoelectron spectroscopy confirmed the presence of iron only as Fe3+ and, moreover, evidenced the presence of a substantial amount of Ti3+ ions in the structure. The presence of both Fe3+ (spin 5/2) in different coordinations as well as Ti3+ (spin 1/2) magnetic ions in B-site positions drives the occurrence of magnetic properties from low temperature to above room temperature, through superexchange Fe3+-O-Fe3+, Fe3+-O-Ti3+ and Ti3+-O-Ti3+ interactions. The finding of coexistent ferroelectric and ferromagnetic properties in these compounds ground the route to facile synthesis of multiferroics by simply doping a classical perovskite ferroelectric material like PbTiO3 with an adequate amount of transition magnetic ions. (C) 2016 Elsevier Ltd. All rights reserved.