Enhanced piezoelectric properties of Mn-modified Bi5Ti3FeO15 for high-temperature applications

Bi₅Ti₃FeO₁₅ (BTF) has recently attracted considerable interest as a typical multiferroic oxide, wherein ferroelectric and magnetic orders coexist. The ferroelectric order of BTF implies its piezoelectricity, because a ferroelectric must be a piezoelectric. However, no extensive studies have been carried out on the piezoelectric properties of BTF. Considering its high ferroelectric-paraelectric phase transition temperature (T_c ~ 761°C), it is necessary to analyze the piezoelectricity and thermal stabilities of BTF, a promising high-temperature piezoelectric material. In this study, lightly manganese-modified BTF polycrystalline oxides are fabricated by substituting manganese ions into Fe³⁺ sites via the conventional solid-state reaction method. X-ray diffraction and Raman spectroscopy analyses reveal that the resultant manganese-modified BTF has an Aurivillius-type structure with m = 4, and that the substitutions of Fe by Mn lead to a distortion of BO₆. The temperature-dependent dielectric properties and direct-current (DC) resistivity measurements indicate that the Mn ions can significantly reduce the dielectric loss tanδ and increase the DC resistivity. The piezoelectricity of BTF is confirmed by piezoelectric constant d₃₃ measurements; it exhibits a piezoelectric constant d₃₃ of 7 pC/N. Remarkably, BTF with 4 mol% of Mn (BTF-4Mn) exhibits a large d₃₃ of 23 pC/N, three times that of unmodified BTF, whereas the Curie temperature T_c is almost unchanged, ~765°C. The increased piezoelectric performance can be attributed to the crystal lattice distortion, decreased dielectric loss tanδ, and increased DC resistivity. Additionally, BTF-4Mn exhibits good thermal stabilities of the electromechanical coupling characteristics, which demonstrates that manganese-modified BTF oxides are promising materials for the use in high-temperature piezoelectric sensors.