Even-Parity Self-Trapped Excitons Lead to Magnetic Dipole Radiation in Two-Dimensional Lead Halide Perovskites

Abstract

Recently, unconventional bright magnetic dipole (MD) radiation was observed from two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs). According to commonly accepted HOIP band structure calculations, such MD light emission from the ground-state exciton should be strictly symmetry forbidden. These results suggest that MD emission arises in conjunction with an as-yet unidentified symmetry-breaking mechanism. In this paper, we show that MD light emission originates from a self-trapped p-like exciton stabilized at energies below the primary electric dipole (ED)-emitting 1s exciton. Using suitable combinations of sample and collection geometries, we isolate the distinct temperature-dependent properties of the ED and MD photoluminescence (PL). We show that the ED emission wavelength is nearly constant with temperature, whereas the MD emission wavelength exhibits substantial red shifts with heating. To explain these results, we derive a microscopic model comprising two distinct parity exciton states coupled to lattice distortions. The model explains many experimental observations, including the thermal red shift, the difference in emission wavelengths, and the relative intensities of the ED and MD emission. Thermodynamic analysis of temperature-dependent PL reveals that the MD emission originates from a locally distorted structure. Finally, we demonstrate unusual hysteresis effects of the MD-emitting state near structural phase transitions. We hypothesize that this is another manifestation of the local distortions, indicating that they are insensitive to phase changes in the equilibrium lattice structure.