Exploring 2D/Quasi-2D Ruddlesden-Popper Perovskite A$_{n+1}$Hf$_n$S$_{3n+1}$ (A = Ca, Sr, and Ba; n = 1-3) for Optoelectronics using Many-Body Perturbation Theory

Abstract: Dimensionality engineering in A${n+1}$B$_n$X${3n+1}$ Ruddlesden-Popper (RP) perovskite phases has emerged as a promising strategy to enhance optoelectronic properties. These properties are highly material-dependent, requiring detailed exploration of electronic, optical, excitonic, transport, and polaronic characteristics. However, the absence of comprehensive studies continues to impede the rational design of high-performance materials. In this work, we investigate the excitonic and polaronic effects in A${n+1}$Hf$_n$S${3n+1}$ (A = Ca, Sr, and Ba; n = 1-3) RP phases, examining their relative stability and optoelectronic properties using several first-principles based methodologies within the framework of density functional theory and many-body perturbation theory (GW and BSE). Our study suggests that these compounds are mechanically stable and feature G$_0$W$_0$@PBE bandgaps ranging from 1.43 to 2.14 eV, which are smaller than those of their bulk counterparts. BSE and model-BSE (mBSE) calculations indicate that these RP phases display notable optical anisotropy, with the exciton binding energy decreasing as the thickness of the perovskite layer increases. In addition, intermediate to strong carrier-phonon scattering is observed in these compounds, confirmed through the Fr\"ohlich mechanism near room temperature. Using the Feynman polaron model, the polaron parameters of these RP phases are also computed, and it is found that charge-separated polaronic states are less stable than bound excitons. Finally, a significant increase in electron mobilities is observed in RP phases compared to their bulk counterparts. Overall, the insights gained from this study will enable the rational design of layered perovskite phases for applications in solar cells and other optoelectronic devices.