Understanding Variations in Circularly Polarized Photoluminescence in Monolayer Transition Metal Dichalcogenides

Monolayer transition metal dichalcogenides are promising materials for valleytronic operations. They exhibit two inequivalent valleys in the Brillouin zone, and the valley populations can be directly controlled and determined using circularly polarized optical excitation and emission. The photoluminescence polarization reflects the ratio of the two valley populations. A wide range of values for the degree of circularly polarized emission, P_circ, has been reported for monolayer WS₂, although the reasons for the disparity are unclear. Here, we optically populate one valley and measure P_circ to explore the valley population dynamics at room temperature in a large number of monolayer WS₂ samples synthesized via chemical vapor deposition. Under resonant excitation, P_circ ranges from 2 to 32%, and we observe a pronounced inverse relationship between photoluminescence (PL) intensity and P_circ. High-quality samples exhibiting strong PL and long exciton relaxation time exhibit a low degree of valley polarization, and vice versa. This behavior is also demonstrated in monolayer WSe₂ samples and transferred WS₂, indicating that this correlation may be more generally observed and account for the wide variations reported for P_circ. Time-resolved PL provides insight into the role of radiative and nonradiative contributions to the observed polarization. Short nonradiative lifetimes result in a higher measured polarization by limiting opportunity for depolarizing scattering events.