(1−x)BiFeO3–(x)Pb(Fe2/3W1/3)O3 ceramics (x = 0.00–0.30) were synthesized by a solid-state reaction route. Structural characterization was done by X-ray diffraction and Raman spectroscopic studies. Existence of rhombohedral symmetry with the \(R3c\) space group up to x ≤ 0.20 and a transition to cubic symmetry with the \(Pm\overline{3 }m\) space group for x > 0.25, confirmed with Rietveld refinement. Raman studies also confirm the significant modification at the A-site due to the replacement of Bi3+ atom by Pb2+ indicating the structural modification in Pb(Fe2/3W1/3)O3 (PFW) in BiFeO3 (BFO). Morphology and microstructure were observed using SEM micrographs and the average grain size was decreased with the increase in PFW concentration (x). Enhanced magnetic and ferroelectric properties were observed up to x ≤ 0.20, which can be attributed to the suppression of spin-canted structure and reduced leakage currents. Hence, BFO–PFW solid ceramics, with a limited low composition region, can be useful for magneto-electric device applications.
