Ferroelectricity in Ruddlesden-Popper Chalcogenide Perovskites for Photovoltaic Application: The Role of Tolerance Factor.

Chalcogenide perovskites with optimal band gap and desirable light absorption are promising for photovoltaic devices, whereas the absence of ferroelectricity limits their potential in applications. On the basis of first-principles calculations, we reveal the underlying mechanism of the paraelectric nature of BaZrS observed in experiments and demonstrate a general rule for the appearance of ferroelectricity in chalcogenide perovskites with Ruddlesden-Popper (RP) ABX structures. Group theoretical analysis shows that the tolerance factor is the primary factor that dominates the ferroelectricity. Both BaZrS and BaHfS with large tolerance factor are paraelectric because of the suppression of in-phase rotation that is indispensable to hybrid improper ferroelectricity. In contrast, CaZrS, CaHfS, CaZrSe, and CaHfS with small tolerance factor exhibit in-phase rotation and can be stable in the ferroelectric Cmc2 ground state with nontrivial polarization. These findings not only provide useful guidance to engineering ferroelectricity in RP chalcogenide perovskites but also suggest potential ferroelectric semiconductors for photovoltaic applications.