Exotic ferroelectricity in strained BaZrS3 chalcogenide perovskite for photovoltaics

Abstract

Abstract Ferroelectricity in solar cells is credited with a multitude of benefits, including improved charge carrier separation and higher than band gap device voltages, however most ferroelectrics are wide-gap materials that generate very little photocurrent. Some halide perovskites are ferroelectric, but they suffer from degradation, despite their otherwise excellent performance. Recently, BaZrS3, a chalcogenide perovskite has received attention due to its optimal band gap, non-toxicity, and superior stability. The ground state of BaZrS3 is reportedly a GdFeO3-type distorted perovskite (space group Pnma). Here, using first-principle calculations, we show that the polar Pna21 is thermodynamically as stable as Pnma. This new phase is weakly ferroelectric, exhibiting a net polarization of 0.27 µC/cm2 and a d 33 piezoelectric coefficient of only ~1 pm/V. Under strain, the interplay between out-of-plane and in-plane octahedral tilts amplifies spontaneous polarization, spin splitting, and large polaron radii. These exotic traits are comparable to those of the popular halide perovskites.