Apparent breakdown of Raman selection rule at valley exciton resonances in monolayer Mo S2

The valley degree of freedom in atomically thin transition metal dichalcogenides (TMDCs) has generated great interest due to the possibility of using it to store and control information in analogy to the spin degree of freedom in spintronics. A signature of the valley pseudospin is the selective coupling of valley excitons to photons with defined helicity. This selectivity can have important consequences for a variety of optical phenomena associated with the valley excitons. Here we report that Raman features that seemingly violate the Raman selection rules can become prominent at valley exciton resonances in atomically thin MoS2. Specifically, the Raman selection rule requires the excitation and scattering photons to have opposite circular polarizations for the in-plane E′ mode phonon, but we observe an apparent E′ Raman peak for excitation and scattered photons with the same circular polarization at exciton resonances. We attribute this peak to a defect-assisted process that involves phonons in the transverse optical E′ branch slightly away from the Γ point, a process that can be enhanced by the selective coupling of valley pseudospin to photon helicity. Thus, the valley pseudospin, in addition to the crystal symmetry, may be important in understanding the Raman scattering spectra for excitations close to valley exciton resonances.