Covalent-like bondings and abnormal formation of ferroelectric structures in binary ionic salts

Abstract

In the Mooser-Pearson diagram, binary ionic compoundss form into nonpolar symmetrical structures with high coordination numbers, while wurtzite structures should appear in the covalent region. Their tetrahedral bonding configurations break the inversion symmetry, with polarizations almost unswitchable due to the high barriers of abrupt breaking and reformation of covalent bonds. Here, through first-principles calculations, we find some exceptional cases of highly ionic ferroelectric binary salts such as lithium halides, which may form into wurtzite structures with covalent-like sp 3 bondings, and the origin of these abnormal formations is clarified. Their high polarizations induced by symmetry breaking are switchable, with much smoother switching pathway refrained from abrupt bond breaking due to the long-range feature of Coulomb interactions. These covalent-like ionic bondings do reduce not only their ferroelectric switching barriers but also the phase transition barriers between polar and nonpolar phases, rendering high performance in applications such as nonvolatile memory and energy storage.