Transition Dipole Moments of n = 1, 2, and 3 Perovskite Quantum Wells from the Optical Stark Effect and Many-Body Perturbation Theory

Abstract

Metal halide perovskite quantum wells (PQWs) are quantum and dielectrically confined materials exhibiting strongly bound excitons. The exciton transition dipole moment dictates absorption strength and influences interwell coupling in dipole-mediated energy transfer - a process that influences the performance of PQW optoelectronic devices. Here we use transient reflectance spectroscopy with circularly polarized laser pulses to investigate the optical Stark effect in dimensionally pure single crystals of n = 1, 2 and 3 Ruddlesden-Popper PQWs. From these measurements, we extract in-plane transition dipole moments of 11.1 (± 0.4), 9.6 (± 0.6) and 13.0 (± 0.8) D for n = 1, 2 and 3, respectively. We corroborate our experimental results with density functional and many-body perturbation theory calculations, finding that the nature of bandedge orbitals and exciton wavefunction delocalization depends on the PQW "odd-even" symmetry. This accounts for the non-monotonic relationship between transition dipole moment and PQW dimensionality in the n = 1 - 3 range.