摘要：Benefiting from strong photon–exciton and phonon–exciton interactions in atomic thickness, transition metal dichalcogenides (TMDCs) are viewed as one promising platform for exploring elementary excitonic photoluminescence (PL) and intrinsic spin–valley properties at the monolayer limit. Despite well-studied Stokes downconversion (DC) PL, the anti-Stokes upconversion (UC) PL has been recently reported in TMDC monolayers, which mainly focus on UC mechanisms while detailed valley-related dynamical processes are unwittingly less concerned. Here, we carry out an in-depth investigation on both DC and UC emission features of monolayer WS2 at room temperature, where UC PL persists with energy gain up to 190 meV. The PL excitation and power-dependent experiments clearly distinguish the origins of DC PL and UC PL, which refer to saturated absorption and phonon-assisted transition from charged trions to neutral A-excitons. And contrast valley properties are observed in DC and UC scenarios with polarization-resolved PL and pump–probe measurements. According to the experimental facts, phenomenological dynamical DC and UC scenarios are modeled with intervalley depolarization taken into consideration, in which intermediates from spontaneous intervalley depolarization account for the observed emission and valley properties. This work can help understand the light–matter interactions and valley properties in monolayer TMDCs.
