Ultrafast Insights into High Energy (C and D) Excitons in Few Layer WS₂

High energy (C and D) excitons possess extraordinary influence over the optical properties of atomically thin transition metal dichalcogenides (TMDCs), and the comprehensive understanding of these would play a pivotal role in advancing research on 2D optoelectronics. Herein, we employed transient absorption spectroscopy to monitor the underlying photophysical processes involved with different excitonic features in few layer WS₂, modeled as a TMDC representative. We observed a strong intervalley coupling across the momentum space and proposed the most plausible relaxation pathway for different excitons in few layer scenario. C and D exciton dynamics were significantly slower as compared to canonical A and B excitons, as a consequence of the indirect Λ-Γ relaxation in C and D and direct K-K combination in A and B. Most importantly, all four excitons emerge in the system and influence each other irrespective of the incident photon energy, which would be extremely impactful in fabricating wide range photonic devices.