The nature of an enhanced ferroelectric phase transition temperature in perovskite-based solid solutions

TL;DR

This paper presents a theoretical explanation for the enhanced ferroelectric phase transition temperature in perovskite solid solutions, attributing it to nonlinear and spatial correlation effects modeled via a random field theory with a key nonlinearity parameter.

Contribution

It introduces a novel theoretical framework incorporating nonlinear effects to accurately predict the transition temperature in ferroelectric solid solutions, with the nonlinearity coefficient as the main adjustable parameter.

Findings

Maximum $T_c$ occurs at positive nonlinearity coefficient.

Enhancing nonlinearity significantly increases $T_c$ beyond end members.

Theory can predict various thermodynamic properties based on composition and external conditions.

Abstract

We explain the phenomena of ferroelectric phase transition temperature $T_c$ enhancement beyond the end members in perovskite solid solutions like BiMeO$_3$-PbTiO$_3$ (Me=Sc, In, etc.) is related to nonlinear and spatial correlation effects. The explanation is based on the calculation of $T_c$ in the framework of our random field theory with additional account for nonlinear effects in the above substances. We show that the maximum of $T_c$ for certain PbTiO$_3$ content takes place when coefficient of nonlinearity is positive, the value of this coefficient is found from best fit between theory and experiment. This nonlinearity coefficient is the only adjustable parameter of the theory. We show that enhancement of positive nonlinearity coefficients enhances greatly the $T_c$ maximum over its value for end members. The theory lays the foundation to calculate not only $T_c$ for above solid solutions but virtually any equilibrium and/or nonequilibrium thermodynamic characteristics such as static and dynamic dielectric susceptibility, specific heat etc as a functions of PbTiO$_3$ content, temperature, electric field and other external parameters.