Ultrafast exciton polaron dynamics in 2D Ruddlesden Popper lead halide perovskites

Abstract

Two dimensional Ruddlesden Popper (2D) RP hybrid perovskites exhibit substantially higher chemical and structural stability than their three dimensional (3D) counterparts, positioning them as promising candidates for next generation optoelectronics. While quasiparticle dynamics in 3D perovskites are well studied, their 2D analogues remain comparatively underexplored. Here we systematically investigate the branching, dynamics, and interactions of free excitons (FEs) and exciton polarons EPs in monolayer 2D RP perovskites using visible range femtosecond transient absorption TA spectroscopy. We prepared monolayer 2D RP perovskite thin films with varied organic spacers and distinct fabrication routes for comparative analysis. We find that the EP binding energy is 50 65 meV in (BA)2PbI4 and 37 39 meV in (PEA)2PbI4, consistent with spacer layer dependent coupling as corroborated by FTIR. We reveal a dynamic equilibrium between FEs and EPs that persists for tens of picoseconds. Notably, the TA signatures differ by fabrication route films from the newly developed process show weaker Auger annihilation and a reduced hot phonon bottleneck than those from the conventional route trends consistent with fewer traps and impurities in the former. Coupled rate equation modeling reproduces the transients and quantifies the processes of hot carrier relaxation, exciton exciton annihilation, exciton phonon coupling, and FE EP interconversion. These results demonstrate that the chemical synthetic process (fabrication route) and spacer choice significantly influence EP stability and population balance, offering practical levers for engineering ultrafast photophysics in 2D perovskites and guiding the design of advanced optoelectronic devices.