Intra- and Interlayer Excitonic Fine Structure of the Two-Dimensional Perovskite (PEA)$_2$PbI$_4$

Abstract: Two-dimensional halide perovskites host strongly bound excitons whose fine structure controls polarization selection rules and radiative recombination, yet several spectral features in (PEA)$_2$PbI$_4$ remain controversially assigned. Here, polarization-resolved low-temperature photoluminescence combined with first-principles G$_0$W$_0$+BSE calculations resolves both the intralayer and interlayer excitonic fine structure of this prototypical n=1 Ruddlesden-Popper perovskite. The low-energy multiplet is consistently described as a purely excitonic intralayer fine structure governed by crystal symmetry, octahedral distortions, and the two-layer unit cell, without invoking Rashba or exciton-polaron mechanisms as the primary origin. A weaker doublet ~45 meV above the bright intralayer states is identified as interlayer excitons from its agreement with the calculated interlayer manifold in energy and splitting. Although the static calculations underestimate their oscillator strength and do not reproduce the observed orthogonal polarizations, distortion-induced mixing with bright intralayer excitons strongly enhances interlayer optical activity and provides a plausible explanation for their visibility. Our results establish interlayer excitons in (PEA)$_2$PbI$_4$ and refine the excitonic description of fine structure in two-dimensional perovskites.