Coupling between ferroelectric distortions and excitonic properties in PbTiO3

Abstract

PbTiO3 is a ferroelectric perovskite semiconductor with favorable electronic and optical properties, making it suitable for a wide range of applications, including photo-catalysis and (opto)electronic devices. Despite its relevance, an accurate ab initio description of the optical absorption spectrum and of the impact of ferroelectric distortion on the excitonic properties is still lacking. We combine G0W0 and Bethe–Salpeter equation calculations to investigate the electronic and optical properties of PbTiO3, tracking the evolution of its excitonic spectrum along the transition from the cubic paraelectric to the tetragonal ferroelectric phase. As the polar distortion increases, the first absorption peak of the cubic phase splits into two distinct features due to symmetry breaking, which partially lifts the degeneracy of the underlying excitonic state. Crucially, the distortion further introduces an in-plane/out-of-plane anisotropy in the spectra and controls the energy separation between the resulting excitonic branches. These findings highlight the potential for tuning the optical absorption properties of PbTiO3 via the application of an external electric field.