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Enhanced domain mobility is considered as one of the importantcharacteristics of morphotropic phase boundary (MPB) ferroelectrics exhibitinga very large piezoelectric response. For nearly two decades, Rayleigh analysisof dielectric and piezoelectric response at sub-coercive fields has been usedas a phenomenological tool to determine the relative contribution of domainwalls in influencing polar properties in these systems. The high value of theextrinsic Rayleigh coefficient at the MPB is generally attributed to enhanceddomain mobility. Using coercive field as a measure of hindrance to domainmobility, in this paper, we have examined the correlation between the extrinsicRayleigh coefficient, piezoelectric response, and coercive field (EC) by acomparative study on three different high performance piezoelectrics (i)(BaTi0.88Sn0.12)-(Ba0.7Ca0.3)TiO3, (ii) Pb(Zr,Ti)O3 and (iii) PbTiO3-BiScO3across their respective MPBs. Our study shows that although the three systemsexhibit maximum piezoelectric response and maximum extrinsic Rayleighcoefficient for their respective MPB compositions, the domain mobility in theMPB compositions of the Pb-based systems is not the highest. The lead-freesystem, on the other hand, exhibits highest domain mobility for the criticalMPB composition. Contrary to the common perception, our study reveals thatlarge value of the Rayleigh coefficient at the MPB is not necessarilyindicative of enhanced domain mobility. We argue that the large piezoresponsein MPB systems is a result of complex interplay of field induced motion of theinterphase boundaries and domain walls. In the lead-based systems theinterphase boundary motion hinders domain wall mobility. The large value of theRayleigh coefficient and piezoresponse in the Pb-based systems is because ofthe dominant role of the interphase boundary motion instead of the enhanceddomain wall mobility.

Extrinsic Rayleigh coefficient and domain mobility in critical MPB compositions of high-performance piezoceramics: A revisit