Intrinsic ferroelectric switching from first principles

The existence of domain walls, which separate regions of different polarization, can influence the dielectric(1), piezoelectric(2), pyroelectric(3) and electronic properties(4,5) of ferroelectric materials. In particular, domain-wall motion is crucial for polarization switching, which is characterized by the hysteresis loop that is a signature feature of ferroelectric materials(6). Experimentally, the observed dynamics of polarization switching and domain-wall motion are usually explained as the behaviour of an elastic interface pinned by a random potential that is generated by defects(7,8), which appear to be strongly sample-dependent and affected by various elastic, microstructural and other extrinsic effects(9-12). Theoretically, connecting the zero-kelvin, first-principles-based, microscopic quantities of a sample with finite-temperature, macroscopic properties such as the coercive field is critical for material design and device performance; and the lack of such a connection has prevented the use of techniques based on ab initio calculations for high-throughput computational materials discovery. Here we use molecular dynamics simulations(13) of 90 degrees domain walls (separating domains with orthogonal polarization directions) in the ferroelectric material PbTiO3 to provide microscopic insights that enable the construction of a simple, universal, nucleation-and-growth-based analytical model that quantifies the dynamics of many types of domain walls in various ferroelectrics. We then predict the temperature and frequency dependence of hysteresis loops and coercive fields at finite temperatures from first principles. We find that, even in the absence of defects, the intrinsic temperature and field dependence of the domain-wall velocity can be described with a nonlinear creep-like region and a depinning-like region. Our model enables quantitative estimation of coercive fields, which agree well with experimental results for ceramics and thin films. This agreement between model and experiment suggests that, despite the complexity of ferroelectric materials, typical ferroelectric switching is largely governed by a simple, universal mechanism of intrinsic domain-wall motion, providing an efficient framework for predicting and optimizing the properties of ferroelectric materials.