A Multilevel Analytical Theory for Prediction of Ferroelectric Perovskite Oxide Properties from Composition

Abstract

Prediction of properties from composition is a fundamental goal of materials science that is particularly relevant for ferroelectric perovskite oxide solid solutions where compositional variation is a primary tool for material design. Design of ferroelectric oxide solid solutions has been guided by heuristics and first‐principles and Landau–Ginzburg–Devonshire theoretical methods that become increasingly difficult to apply in ternary, quaternary, and quintary solid solutions. To address this problem, a multilevel model is developed for the prediction of the ferroelectric‐to‐paraelectric transition temperature (Tc), coercive field (Ec), and polarization (P) of PbTiO3‐derived ferroelectric solid solutions from composition. The characteristics of the materials at different length scales, starting at the level of the electronic structure and chemical bonding of the constituent ions and ending at the level of collective behavior, are analytically related by using ferroelectric domain walls and cationic off‐center displacements as the key links between the different levels of the model. The obtained composition–structure–property relationships provide a unified quantitatively predictive theory for understanding PbTiO3‐derived solid solutions. Such a multilevel analytical modeling approach is likely to be generally applicable to different classes of ferroelectric perovskite oxides and to other functional properties, and to materials and properties beyond the field of ferroelectrics.

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“…[31,45] This relationship has also been validated by plotting the E c of several ferroelectric ceramics and single crystals as a function of T c based on experimental data. [39] In particular, the fit for the data of single crystals has shown a better agreement between prediction and [46] Copyright 2018, Springer Nature. b) Schematics of a multilevel model for predicting ferroelectric properties of Pb-based perovskite oxide solid solutions.…”

“…Figure 4 depicts that Equation 12 has worked better for Pb‐ and Bi‐based perovskite oxide solid solutions. [ 39 ] Despite the better fitting, Equation 12 has caused some confusion because it suggests that a material without any intrinsic polarization would still possess a ‘‘ T c, ’’ which is not in line with the common perception of physical rules. There must be unknown factors, which require further investigation in revised or new models.…”

“…The macroscopic properties include polarization (P), domain wall energies (𝜎 𝜃 ), Curie Temperature (T c ), and coercive field (E c ). Reproduced with permission [39]. Copyright 2022, John Wiley and Sons.…”

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“…Several composition–structure property correlations have been recently used to create a model for predicting collective properties of PbTiO 3 -derived solid solutions . However, these correlations cannot be generalized to Pb-free ferroelectric materials.…”

“…Several composition−structure property correlations have been recently used to create a model for predicting collective properties of PbTiO 3 -derived solid solutions. 24 However, these correlations cannot be generalized to Pb-free ferroelectric materials. By contrast, the same DFT calculations have been widely used to study both lead-based and lead-free ferroelectric solid solutions.…”