Franz-Keldysh and Stark Effects in Two-Dimensional Metal Halide Perovskites

As the field of metal halide perovskites (MHP) matures, state-of-the-art techniques to measure basic properties such as the band gap and exciton binding energy continue to produce inconsistent values. This issue is persistent even for 2D MHPs wherein the large separation between exciton and continuum states should make such measurements more straightforward. In this study, we revert to the established theory of a 2D Wannier exciton in a uniform electric field to analyze the electroabsorption response of an archetypal 2D MHP system, phenethylammonium lead iodide (PEA2PbI4). The high level of agreement between the electroabsorption simulation and measurement allows for a deepened understanding of the exciton's redshift according to the quadratic Stark effect and the continuum wavefunction leaking according to the Franz-Keldysh effect. We find the field-dependency of each of these effects to be rich with information, yielding measurements of the exciton's Bohr radius, transition dipole moment, polarizability, and reduced effective mass. Most importantly, the exciton binding energy is unambiguously determined with 2% uncertainty. The high precision of these new measurement methods opens the opportunity for future studies to accurately determine the influence of chemical and environmental factors on the optoelectronic properties of MHPs and thereby increase the tunability of this important class of materials.