Abstract
This work investigates the role of A-site chemical bonding in morphotropic phase boundary (MPB) compositions of PbTiO3–BiFeO3 solid solutions exhibiting high tetragonality. Ba substitution significantly reduces the ferroelectric critical temperature, which correlates well with the structural parameters and manifests marked change in the free energy profile of structural phases within the MPB regime. A reduction in the grain size with Ba substitution has been observed which shows the reduction in the grain growth with Ba incorporation. The presence of pinned defect dipoles has been confirmed from the observed elliptical hysteresis loops at room temperature, making high-temperature permittivity studies unique to unraveling the finer details of this system. Inter and Intra grain contributions in the electrical response are quantified from the equivalent circuit analysis and compared with the complex permittivity profile. The frequency and temperature-dependent ac conductivity responses were analyzed, and observed conductivity was related to charge carriers hopping between vacant sites.
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