Ferroelectricity and antiferroelectricity in the BaS-PbS system with the rocksalt structure

Abstract

The ferroelectric instability in superstructures, superlattices, quantum wires, and disordered solid solutions in the BaS--PbS system with the NaCl structure has been discovered and investigated using first-principles calculations within the density functional theory. The emergence of ferroelectricity in these structures is associated with the instability of TO phonons in linear --Pb--S--Pb--S-- chains, which arises as a result of stretching of the structures upon the introduction of large barium atoms. Additionally, it has been discovered that, alongside ferroelectric phases, the structures also exhibit stable, competing antiferroelectric phases and those with a mixed ferroelectric--antiferroelectric ordering (ferroelectrically polarized one-dimensional Pb--S chains arranged in an ordered or disordered manner in the perpendicular direction). These phases often become the ground state of the studied systems. The closeness of the energies of the ferroelectric, antiferroelectric, and mixed states indicates the emergence of a multi-minimum potential with an infinite number of wells separated by potential barriers in the configuration space. This suggests a possible emergence of nonergodicity in the structures at low temperatures.