Double polarization hysteresis and dramatic influence of small compositional variations on the electrical properties in Bi₄Ti₃O₁₂ ceramics

This work reports the existence of double polarization hysteresis (P–E) loop in Aurivillius-phase ferroelectric Bi₄Ti₃O₁₂ (BiT) and reveals dramatic influence of small compositional variations on the electrical properties of it. The double polarization hysteresis is a characteristic of the interaction of defects with domain walls. This characteristic becomes more pronounced in Bi-deficient and Mg-doped BiT due to an increase in oxygen vacancy concentration at the lattices. Normal and saturated P–E loop is recalled by Nb donor doping, and associated composition Bi₄Ti_2.97Nb_0.03O_12.015 (BiT-0.03Nb) shows high remnant polarization (P_r = 12.5 μC/cm²) and large field-induced strain (S₃₃ = 5.6 × 10⁻⁴). In addition, this doping results in bulk conductivity (σ_b) of BiT decreasing dramatically and associated activity energy (E_a) increasing significantly. In contrast, high oxide ion conductivity is induced with Mg²⁺ acceptor doping, and at 600 °C the optimum composition has ionic conductivity of ˜0.65 × 10⁻² S cm⁻¹ in the bulk.