Activated Migration of Localized Ligand-Field Excitons in Atomically Thin CrCl3

Abstract Two-dimensional crystals with densely packed atoms exhibit a range of emerging properties, particularly a wide variety of excitonic behaviors. Thickness-variable layered chromium trihalides with finite surface recombination sites provide an ideal system for understanding how excitons confined in octahedral ligand fields migrate on nanometer length scales, a regime that defies conventional transport probes. In this work, we demonstrate that Cr3+-derived photoluminescence in CrCl3 is spectrally independent of thickness, but its relaxation dynamics are strongly sensitive to thickness and temperature, thereby indicating significant activated migration. A diffusion-coupled surface recombination model reveals an effective out-of-plane diffusion coefficient of 4.5 × 10–6 cm2/s for the ligand-field excitons and a diffusion activation energy of 130 meV. A quantitative Forster analysis yields a diffusion coefficient comparable to the experimental value, supporting long-range dipolar energy transfer as a plausible mechanism for interlayer exciton migration. The activation energy is comparable to the reorganization energy independently estimated from optical Stokes shifts, suggesting that exciton transport is coupled to local lattice relaxation. Furthermore, we show that the relaxation dynamics can be systematically tuned by either enhancing or suppressing surface recombination through controlled surface reactions or encapsulation. This work not only reveals the nanoscopic transport of localized ligand-field excitons but also establishes a spectroscopic transport probe applicable to various 2D materials.