DFT-based insight into finite-temperature properties of ferroelectric perovskites with lone-pair: the case of CsGeX ₃ (X = Cl, Br, I)

Ferroelectrics remain in the focus of scientific attention for decades owing to their fundamental and practical appeal. Recently, ferroelectricity has been demonstrated in semiconducting halide perovskites (Zhang<i>et al</i>2022<i>Sci. Adv.</i><b>8</b>eabj5881), offering both a rare combination of ferroelectricity and semiconductivity in the same material and a possible alternative to the prevailing perovskite oxide ferroelectrics. We propose a route to simulating such materials at finite temperatures capable of reproducing key experimental and first-principle data, such as Curie temperature, phase transition sequence, spontaneous polarization, and soft mode frequencies. The key methodological finding is the superior performance of hybrid exchange correlation functionals in parametrization of effective Hamiltonians for ferroelectrics with lone pair. The parametrization for effective Hamiltonians for CsGeX₃ (X = Cl, Br, I) is reported. The application of methodology to study polarization reversal in CsGeX₃ allows for the development of a 'minimalistic' model for polarization reversal in ferroelectrics that provides an insight into the mechanisms of polarization reversal and its key features, such as the relationship between the coercive field, temperature, and AC field frequency. Importantly, the model reveals the origin of the well-known and ever-puzzling overestimation of coercive fields in computations. Furthermore, we report a variety of finite-temperature properties of CsGeX₃ ferroelectrics, such as dielectric susceptibility, pyroelectric coefficients, and energy storage density, which reveal that these halide perovskites possess properties comparable to their oxide counterparts. We believe that our work provides significant methodological advancements, deepens fundamental understanding of ferroelectrics, and reveals the potential of halide perovskite ferroelectrics.