Narrow-Linewidth Emission and Weak Exciton-Phonon Coupling in 2D Layered Germanium Halide Perovskites

The photophysical properties of low-dimensional metal-halide semiconductors and their tunability make them promising candidates for light-absorbing and emitting applications. Yet, the germanium-based halide perovskites to date lack desirable light-emitting properties, with so far only very broad, weak, and unstructured photoluminescence (PL) reported due to significant octahedral distortion. Here, the photophysical properties of the 2D layered Ruddlesden-Popper semiconductors (4F-PMA)₂GeI₄ and (4F-PMA)₂PbI₄ (4F-PMA: 4-F-phenylmethylammonium) are characterized and compared. Using a combination of single-crystal X-ray diffraction, variable temperature time-resolved PL, and density functional theory, structure-property relations are correlated. Specifically, the results indicate that (4F-PMA)₂PbI₄ features stronger coupling to longitudinal optical (LO) phonons, assisting emission from a broad bound-exciton state due to a soft, deformable lattice. In contrast, (4F-PMA)₂GeI₄, benefitting from intermolecular bonding to scaffold a rigid octahedral structure, shows weaker LO-phonon coupling, resulting in the longest PL lifetime and most narrow linewidth (≈120 meV linewidth at 2 K) reported for a Ge-halide perovskite yet, without the occurrence of any additional bound-state emission at low temperatures. These results highlight the potential of germanium halide perovskite materials for optoelectronic applications.