Photoluminescence Path Bifurcations by Spin Flip in Two-Dimensional CrPS4

Ultrathin layered crystals of coordinated chromium-(III) are promising not only as two-dimensional (2D) magnets but also as 2D near-infrared (NIR) emitters due to long-range spin correlation and efficient transition between high-and low-spin excited states of Cr3+ ions. In this study, we report on the dual-band NIR photoluminescence (PL) of CrPS4 and show that its excitonic emission bifurcates into fluorescence and phosphorescence depending on thickness, temperature, and defect density. In addition to the spectral branching, the biexponential decay of PL transients, also affected by the three factors, could be well described within a three-level kinetic model for Cr(III). In essence, the PL bifurcations are governed by activated reverse intersystem crossing from the low- to high-spin states, and the transition barrier becomes lower for thinner 2D samples because of surface-localized defects. Our findings can be generalized to 2D solids of coordinated metals and will be valuable in realizing groundbreaking magneto-optic functions and devices.

Automated summary

This study reports the dual-band near-infrared photoluminescence of CrPS4 crystals and reveals that its emission splits into fluorescence and phosphorescence depending on thickness, temperature, and defect density. The bifurcation of the emission is controlled by activated reverse intersystem crossing from low- to high-spin states, and the transition barrier becomes lower for thinner 2D samples due to surface-localized defects. These findings have important implications for realizing groundbreaking magneto-optic functions and devices in coordinated metals' 2D solids.