Exploring Exciton and Polaron Dominated Photo-physical Phenomena in Ruddlesden-Popper Phases of Ban+1ZrnS3n+1 (n=[1-3]) from Many Body Perturbation Theory

Abstract

Ruddlesden-Popper (RP) phases of Ba n+1 Zr n S 3n+1 (n=[1-3]) are evolved as new promising class of chalcogenide perovskites in the field of optoelectronics, especially in solar cells.However, detailed studies regarding its optical, excitonic, polaronic and transport properties are hitherto unknown. Here, we have explored the excitonic and polaronic effect in RP phases of Ba n+1 Zr n S 3n+1 (n=[1-3]) using several first-principles based state-of-the-art methodologies under the framework of Many Body Perturbation Theory. Unlike it's bulk counterpart, the optical and excitonic anisotropy are observed in Ba n+1 Zr n S 3n+1 (n=[1-3]) RP phases. From Wannier-Mott approach, we show that in the RP phases of this class of chalcogenide perovskites, capturing the ionic contribution to the dielectric constant is important. We report significant ionic contribution and relatively smaller electron-phonon coupling constant for Ba n+1 Zr n S 3n+1 in comparison to the bulk BaZrS 3 . The exciton binding energy is found to be dependent on the presence of large electron-phonon coupling. The charge carrier mobility is maximum in Ba 2 ZrS 4 , computed employing deformation potential of the same. As per our analysis, the optical phonon modes are observed to dominate the acoustic phonon modes, leading to decrease in polaron mobility on increasing n in Ba n+1 Zr n S 3n+1 (n=[1-3]).