Coupling between ferroelectric distortions and excitonic properties in PbTiO$_3$

Abstract

PbTiO$_3$ is a ferroelectric perovskite semiconductor with favourable 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 $G_0W_0$ and Bethe-Salpeter Equation calculations to investigate the electronic and optical properties of PbTiO$_3$, 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 PbTiO$_3$ via the application of an external electric field.