Rapid Spin Depolarization in the Layered 2D Ruddlesden-Popper Perovskite (BA)(MA)PbI.

We report temperature-dependent spectroscopy on the layered (n = 4) two-dimensional (2D) Ruddlesden-Popper perovskite (BA)(MA)PbI. Helicity-resolved steady-state photoluminescence (PL) reveals no optical degree of polarization. Time-resolved PL shows a photocarrier lifetime on the order of nanoseconds. From simultaneously recorded time-resolved differential reflectivity (TRΔR) and time-resolved Kerr ellipticity (TRKE), a photocarrier lifetime of a few nanoseconds and a spin relaxation time on the order of picoseconds was found. This stark contrast in lifetimes clearly explains the lack of spin polarization in steady-state PL. While we observe clear temperature-dependent effects on the PL dynamics that can be related to structural dynamics, spin relaxation is nearly T-independent. Our results highlight that spin relaxation in 2D (BA)(MA)PbI occurs at time scales faster than the exciton recombination time, which poses a bottleneck for applications aiming to utilize this degree of freedom.

Strong quenching of dye fluorescence in monomeric perylene orange/TMDC hybrid structures.

Hybrid structures with an interface between two different materials with properly aligned energy levels facilitate photo-induced charge separation to be exploited in optoelectronic applications. Particularly, the combination of 2D transition metal dichalcogenides (TMDCs) and dye molecules offers strong light-matter interaction, tailorable band level alignments, and high fluorescence quantum yields. In this work, we aim at the charge or energy transfer-related quenching of the fluorescence of the dye perylene orange (PO) when isolated molecules are brought onto monolayer TMDCs via thermal vapor deposition. Here, micro-photoluminescence spectroscopy revealed a strong intensity drop of the PO fluorescence. For the TMDC emission, in contrast, we observed a relative growth of the trion versus exciton contribution. In addition, fluorescence imaging lifetime microscopy quantified the intensity quenching to a factor of about 103 and demonstrated a drastic lifetime reduction from 3 ns to values much shorter than the 100 ps width of the instrument response function. From the ratio of the intensity quenching that is attributed to hole or energy transfer from dye to semiconductor, we deduce a time constant of several picoseconds at most, pointing to an efficient charge separation suitable for optoelectronic devices.