Few-layered transition-metal dichalcogenides (TMDs) are increasingly popular materials for optoelectronics and catalysis. Among the various types of TMDs available today, rhenium chalcogenides (ReX2) stand out due to their remarkable electronic structure, such as the occurrence of anisotropic excitons and potential direct band gap behavior throughout multilayered stacks. In this paper, we have analyzed the nature and dynamics of charge carriers in highly crystalline liquid-phase exfoliated ReS2, using a unique combination of optical pump-THz probe and broad-band transient absorption spectroscopy. Two distinct time regimes are identified, both of which are dominated by unbound charge carriers despite the high exciton binding energy. In the first time regime, the unbound charge carriers cause an increase and a broadening of the exciton absorption band. In the second time regime, a peculiar narrowing of the excitonic absorption profile is observed, which we assign to the presence of built-in fields and/or charged defects. Our results pave the way to analyze spectrally complex transient absorption measurements on layered TMD materials and indicate the potential for ReS2 to produce mobile free charge carriers, a feat relevant for photovoltaic applications.

2D materials are considered for applications that require strong light-matter interaction because of the apparently giant oscillator strength of the exciton transitions in the absorbance spectrum. Nevertheless, the effective oscillator strengths of these transitions have been scarcely reported, nor is there a consistent interpretation of the obtained values. Here, we analyse the transition dipole moment and the ensuing oscillator strength of the exciton transition in 2D CdSe nanoplatelets by means of the optically induced Stark effect (OSE). Intriguingly, we find that the exciton absorption line reacts to a high intensity optical field as a transition with an oscillator strength F_Stark that is 50 times smaller than expected based on the linear absorption coefficient. We propose that the pronounced exciton absorption line should be seen as the sum of multiple, low oscillator strength transitions, rather than a single high oscillator strength one, a feat we assign to strong exciton center-of-mass localization. Within the quantum mechanical description of excitons, this 50-fold difference between both oscillator strengths corresponds to the ratio between the coherence area of the exciton’s center of mass and the total area, which yields a coherence area of a mere 6.1 nm². Since we find that the coherence area increases with reducing temperature, we conclude that thermal effects, related to lattice vibrations, contribute to exciton localization. In further support of this localization model, we show that F_Stark is independent of the nanoplatelet area, correctly predicts the radiative lifetime, and lines up for strongly confined quantum dot systems. [Figure not available: see fulltext.]