Polycrystalline sample of lead-free 0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃ ceramic has been synthesized by solid state reaction method. Single-phase perovskite structure with rhombohedral symmetry was confirmed by x-ray diffraction. Temperature dependent dielectric permittivity studies demonstrated frequency independent behavior, indicating that the studied sample was not a typical relaxor ferroelectric. A polymorphic phase transition between rhombohedral and tetragonal phase was noticed near room temperature followed by a tetragonal to cubic transition with 97 °C as the temperature of maximum permittivity. The macroscopic values of d₃₃ and d₃₁ were ∼350 pC/N and −141 pm/V, whereas the electromechanical coupling factors k_p and k_t were 44.5% and 41.6%, respectively. Bulk P-E hysteresis loop was obtained with saturation polarization 11 μC/cm² and coercive field ∼4 kV/cm. Distinct polarization contrast with a complex mosaic-like domain structure was observed in the out-of-plane mode of piezoresponse force microscopy. The domain width and the correlation length were estimated to be nearly 2 μm and 827 nm, respectively. Local hysteresis loop with apparent coercive voltage, V_c = 15.8 V, was observed.

Pristine (BiFeO₃), Pr and Sc co-substituted Bi_0.9Pr_0.1Fe_1−x Sc _x O₃ (0.01 ⩽ x ⩽ 0.07) ceramics have been investigated for their structural (including x-ray diffraction and Raman), morphological and piezoresponse behaviour. Secondary phases observed in pristine BiFeO₃ (BFO) ceramic were significantly suppressed in the co-substituted samples. Grain size decreased in the co-substituted samples. Raman study revealed ten active phonon modes which remained almost invariant with co-substitution. Out-of-plane piezoresponse (OPP-PFM) exhibited negative self-polarization effect in the virgin state (without any poling) which has been explained in terms of built-in electric field. The self-polarization effect is largest in 3% Sc co-substituted sample. Poling with ±30 V dc voltage demonstrated both positive and negative domains. Maximum difference in the peak values (from histograms) of such opposite domains was observed in the Bi_0.9Pr_0.1Fe_0.99Sc_0.01O₃ sample. Information from local measurements (such as PFM) should be useful in deciding such multiferroic materials for device application.