Piezoelectric anisotropy and free energy instability in classic perovskites

Several members of the perovskite family are investigated: the temperature dependence of dielectric, elastic, piezoelectric and coupling coefficients of KNbO3 in its orthorhombic ferroelectric phase is determined experimentally; the values of dielectric stiffness coefficients at constant stress, α, are estimated for the 6th order Landau-Ginzburg-Devonshire phenomenological description of KNbO3; the origins of the enhanced piezoelectric responses along non polar directions in perovskites are investigated by studying phenomenologically the temperature evolution of the piezoelectric anisotropy in a material with a sequence of ferroelectric-ferroelectric phase transitions (BaTiO3) and in a material with only one ferroelectric phase (PbTiO3); the influence of external bias fields on piezoelectric response and its anisotropy in ferroelectric perovskites is discussed phenomenologically by studying tetragonal BaTiO3, PbTiO3 and Pb(Zr,Ti)O3 under electric bias field applied anti-parallel to the spontaneous polarization and uniaxial compressive bias stress along the polarization direction; a discussion about a common underlying thermodynamic process able to generally describe the enhancement of the piezoelectric response and its anisotropy is given by investigating the Gibbs free energy flattening in tetragonal BaTiO3, PbTiO3 and Pb(Zr,Ti)O3 upon changes of temperature, bias fields and composition. The main conclusions resulting from this work are: a comparison of the results of electromechanical properties measurements on KNbO3 obtained in this work, the ones found in the literature, and estimates using LGD phenomenology from this work gives discrepancies that suggest that published measurements should be redone; in the absence of bias fields, the intrinsic origin of the enhanced piezoelectric responses in perovskites is the anticipation of a phase transition, no matter what is the cause of that transition (temperature, composition); in the presence of sufficiently high bias fields, an enhanced piezoelectric response along non-polar direction can be predicted in some materials (PbTiO3 under high uniaxial compressive stress along the polar direction); the influence of the external bias fields on electromechanical properties of perovskites may generally be of significant importance: if the electric fields applied anti-parallel to the spontaneous polarization or the uniaxial compressive bias stresses applied along the polarization axis are high enough, the perovskite system can be strongly dielectrically softened (metastable state), increasing the values of dielectric permittivities and piezoelectric coefficients; in the vicinity of a coercive field or a phase transition these electromechanical coefficients can increase by several orders of magnitude; the flattening of the Gibbs free energy profile of each of examined perovskite systems, regardless of whether this flattening is caused by temperature or composition variation, or by applying compressive pressure or antiparellel electric field bias, leads to enhancements of dielectric susceptibilities and of the piezoelectric response; the anisotropy of the free energy flattening is the origin of the anisotropic enhancement of the piezoelectric response, which can occur either by polarization rotation or by polarization contraction.