Origin of Dopant-Carrier Exchange Coupling and Excitonic Zeeman Splitting in Mn²⁺-Doped Lead Halide Perovskite Nanocrystals.

Abstract

Low-dimensional metal halide perovskites have unique optical and electrical properties that render them attractive for the design of diluted magnetic semiconductors. However, the nature of dopant-exciton exchange interactions that result in spin-polarization of host-lattice charge carriers as a basis for spintronics remains unexplored. Here, we investigate Mn²⁺-doped CsPbCl₃ nanocrystals using magnetic circular dichroism spectroscopy and show that Mn²⁺ dopants induce excitonic Zeeman splitting which is strongly dependent on the nature of the band-edge structure. We demonstrate that the largest splitting corresponds to exchange interactions involving the excited state at the M-point along the spin-orbit split-off conduction band edge. This splitting gives rise to an absorption-like <i>C</i>-term excitonic MCD signal, with the estimated effective <i>g</i>-factor (<i>g</i>_eff) of ca. 70. The results of this work help resolve the assignment of absorption transitions observed for metal halide perovskite nanocrystals and allow for a design of new diluted magnetic semiconductor materials for spintronics applications.