Spin‐Valley Polarization Control in WSe₂ Monolayers using Photochemical Doping

Abstract The influence of a photochemical doping method on the spin‐valley polarization degree ( P c ) of excitons in WSe 2 monolayers is reported. By varying the carrier density and transitioning from an excess of electrons (n‐type) to an excess of holes (p‐type), a non‐monotonic dependence of P c on the doping level is observed. Using controlled, single‐shot photochlorination steps, this non‐monotonic behavior is unveiled, with P c reaching a minimum value of less than 10% at 78 K near the charge neutrality point, while increasing by a factor of three at a hole density of 5 × 10 11 cm −2 . The impact of the doping on P c is explained using a phenomenological model that accounts for various mechanisms influencing exciton polarization dynamics, including exciton‐carrier scattering processes and exciton‐to‐trion conversion rates. Among these, exciton‐carrier collisions emerge as the dominant mechanism driving the observed variations in P c , while the exciton effective lifetime remains nearly independent of doping. These findings highlight the potential of photochemical methods for investigating valley physics and for effectively tuning the exciton polarization degree in transition metal dichalcogenide monolayers.