Indirect‐To‐Direct Bandgap Crossover and Room‐Temperature Valley Polarization of Multilayer MoS₂ Achieved by Electrochemical Intercalation

Abstract Monolayer (1L) group VI transition metal dichalcogenides (TMDs) exhibit broken inversion symmetry and strong spin‐orbit coupling, offering promising applications in optoelectronics and valleytronics. Despite their direct bandgap, high absorption coefficient, and spin‐valley locking in K or K’ valleys, the ultra‐short valley lifetime limits their room‐temperature applications. In contrast, multilayer TMDs, with more absorptive layers, sacrifice the direct bandgap and valley polarization upon gaining inversion symmetry from the bilayer structure. Here, we demonstrate that multilayer molybdenum disulfide (MoS₂) can maintain 1) a structure with broken inversion symmetry and strong spin‐orbit coupling, 2) a direct bandgap with high photoluminescence (PL) intensity, and 3) stable valley polarization up to room temperature. Through the intercalation of organic 1‐ethyl‐3‐methylimidazolium (EMIM⁺) ions, multilayer MoS₂ not only exhibits layer decoupling but also benefits from an electron doping effect. This results in a hundredfold increase in PL intensity and stable valley polarization, achieving 55% and 16% degrees of valley polarization at 3 K and room temperature, respectively. The persistent valley polarization at room temperature, due to interlayer decoupling and trion dominance facilitated by a gate‐free method, opens up potential applications in valley‐selective optoelectronics and valley transistors.