Optoelectronic properties of three PbSe polymorphs

Abstract The narrow bandgap PbSe has attracted a remarkable interest from the researchers in recent years for their potential optoelectronics and photovoltaic applications. In this article, we report the optoelectronic properties of cubic (NaCl-type) and orthorhombic (Cmcm- and Pnma-type) polymorphs of PbSe using the density functional theory based first-principles approaches. In accordance with the available literature, the NaCl–PbSe has been found stable in the ground state, whereas the Cmcm-, Pnma-types of PbSe have been realized at intermediate pressure of ~4.5 GPa. The electronic structures and optical spectra of these polymorphs have been determined using the Tran-Blaha modified Becke-Johnson exchange potential with and without spin-orbit coupling (SOC) effects. The inclusion of SOC has shown important effects on the electronic structures and consequently on the optical spectra. Despite SOC driven energy gap narrowing of these polymorphs, the direct bandgap nature of Cmcm-PbSe calculated with TB-mBJ has changed to indirect nature with the inclusion of SOC. Moreover, our results of the optical spectra of NaCl–PbSe have shown that this phase is isotropic, whereas a sufficiently high degree of anisotropy in the optical spectra has been recorded for Cmcm-, Pnma-types of PbSe. These PbSe polymorphs exhibited a high optical absorption that approaches as large as 106 cm−1. Moreover, our study provides comprehensive details of exciton binding energies and plasmon energies. This work is believed to provide a strong foundation to exploit the optoelectronic character of the studied phases of PbSe for next-generation optoelectronic and photovoltaic applications.