• Energy Research
• 2016-2025close

AbstractOne of the open challenges of spintronics is to control the spin relaxation mechanisms. Layered metal-halide perovskites are an emerging class of semiconductors which possess a soft crystal lattice that strongly couples electronic and vibrational states and show promise for spintronic applications. Here, we investigate the impact of such strong coupling on the spin relaxation of excitons in the layered perovskite BA2FAPbI7 using a combination of cryogenic Faraday rotation and transient absorption spectroscopy. We report an unexpected increase of the spin lifetime by two orders of magnitude at 77 K under photoexcitation with photon energy in excess of the exciton absorption peak, and thus demonstrate optical control over the dominant spin relaxation mechanism. We attribute this control to strong coupling between excitons and optically excited phonons, which form polaronic states with reduced electron-hole wave function overlap that protect the exciton spin memory. Our insights highlight the special role of exciton-lattice interactions on the spin physics in the layered perovskites and provide a novel opportunity for optical spin control.

Excitation energy transfer from peridinin to chlorophyll (Chl) a is unusually efficient in the peridinin-chlorophyll a protein (PCP) from dinoflagellates. This enhanced performance is derived from the long intrinsic lifetime of 4.4 ps for the S2 (11Bu+) state of peridinin in PCP, which arises from the electron-withdrawing properties of its carbonyl substituent. Results from heterodyne transient grating spectroscopy indicate that S2 serves as the donor for two channels of energy transfer: a 30 fs process involving quantum coherence and delocalized peridinin-Chl states and an incoherent, 2.5 ps process initiated by dynamic exciton localization, which accompanies the formation of a conformationally distorted intermediate in 45 fs. The lifetime of the S2 state is lengthened in PCP by its intramolecular charge-transfer character, which increases the system-bath coupling and slows the torsional motions that promote nonradiative decay to the S1 (21Ag-) state.

Using circularly polarized broadband transient absorption, time-resolved circular photoluminescence, and transient Faraday rotation spectroscopy, we report that spin-dependent interactions have a significant impact on exciton energies and spin depolarization times in layered Ruddlesden-Popper hybrid metal-halide perovskites. In BA2FAPb2I7, we report that room-temperature spin lifetimes are largest (3.2 ps) at a carrier density of ∼1017 cm-3 with increasing depolarization rates at higher exciton densities. This indicates that many-body interactions reduce spin-lifetimes and outcompete the effect of D'yakonov-Perel precessional relaxation that has been previously reported at lower carrier densities. We further observe a dynamic circular dichroism that arises from a photoinduced polarization in the exciton distribution between total angular momentum states. Our findings provide fundamental and application relevant insights into the spin-dependent exciton-exciton interactions in layered hybrid perovskites.