Enhanced functionalities of isovalently substituted 0.67(Bi1-xLaxFe0.97Ga0.03O3)-0.33(BaTiO3) relaxor piezoceramics synthesized via air quenching

Abstract

The isovalently substituted lead-free binary solid solution, 0.67(Bi1-xLaxFe0.97Ga0.03O3)-0.33(BaTiO3) (BF-BT) (x ≤ 0.07), has been synthesized by solid state ceramic method via air quenching sintering. FTIR and XRD along with Rietveld structure refinement confirmed a pure perovskite phase with a pseudocubic structure (space group Pm3‾m) for developed compositions. SEM revealed a dense microstructure with fine grain size (<1.5 μm) and minimal porosity. XPS analysis reveals predominantly Bi+3 and Fe+3 states, along with oxygen vacancies (VO··). Ferroelectric studies demonstrated a maximum remanent polarization (Pr) of 12.3 μC/cm2 and coercive field EC of 30.95 kV/cm for La3+ concentration of x = 0.03. Overall decrement in Pr can be attributed to dipolar defect-induced random fields reducing the activation barrier for domain nucleation. Leakage current measurement reveals improved resistivity (∼108 Ω cm) up to an applied field of 30 kV/cm. Dielectric measurements unveiled two frequency-dependent anomalies in temperature dependence above room temperature, indicative of diffuse phase transitions. The Vogel-Fulcher model depicted an increasing freezing temperature (from 465 K for x = 0.01–551 K for x = 0.07) and decreasing activation energy (from ∼0.61 eV to 0.07 eV) with increasing La3+ concentration. The estimated diffuseness parameter around ∼2 suggested relaxor behavior. Doping with La resulted in increased dielectric permittivity at 10 kHz (from 4100 to 24066), showcasing the efficacy of site engineering in augmenting the functional properties of BF-BT for high-temperature dielectric and transducer applications.