Resonant Raman signatures of bright and momentum-dark exciton coupled by intervalley phonon scattering in monolayer WSe2

Abstract

Exciton-phonon coupling in atomically thin transition metal dichalcogenides governs key processes such as exciton thermalization and intervalley scattering and remains challenging to access directly by optical spectroscopy. Here, we employ resonance Raman spectroscopy at cryogenic temperatures to probe exciton-phonon coupling in hBN-encapsulated WSe_2 monolayers. Tuning the excitation laser across the bright exciton X_KK resonance, we observe rich Raman spectra and focus on the resonance profile of the degenerate A_1'/E' optical phonon mode. The profile exhibits two asymmetric resonance peaks whose energetic separation significantly exceeds the phonon energy - a feature that cannot be explained by first-order Raman scattering alone. We demonstrate that this discrepancy is resolved by including third-order Raman scattering, in which intervalley scattering enabled by a finite-momentum phonon couples the bright exciton X_KK to a momentum-dark exciton X_d. Fitting the experimental resonance profiles of two independent samples with a model comprising coherent first- and third-order scattering yields consistent exciton energies and linewidths, with a momentum-dark exciton X_d approximately 45meV to 55meV below the bright exciton X_KK. The results indicate efficient bright-to-dark exciton coupling. Our findings provide a microscopic framework for understanding the anomalously bright emission spectra of WSe_2 monolayers despite its spin-forbidden lowest exciton transition and highlight the role of momentum-dark excitons in resonant light-matter interaction.