Photoexcitation Dynamics and Long‐Lived Excitons in Strain‐Engineered Transition Metal Dichalcogenides

Abstract Strain‐engineering in 2D transition metal dichalcogenide (TMD) semiconductors has garnered intense research interest in tailoring the optical properties via strain‐induced modifications of the electronic bands in TMDs, while its impact on the exciton dynamics remains less understood. To address this, an extensive study of transient optical absorption (TA) of both W‐ and Mo‐based single‐crystalline monolayer TMDs grown by a recently developed laser‐assisted evaporation method is performed. All spectral features of the monolayers as grown on fused silica substrates exhibit appreciable redshifts relating to the existence of strain due to growth conditions. Moreover, these systems exhibit a dramatic slowing down of exciton dynamics (100s of picoseconds to few nanoseconds) with an increase in carrier densities, which strongly contrasts with the monolayers in their freestanding form as well as in comparison with more traditionally grown TMDs. The observations are related to the modifications of the electronic bands as expected from the strain and associated population of the intervalley dark excitons that can now interplay with intravalley excitations. These findings are consistent across both the Mo‐ and W‐based TMD families, providing key information about the influence of the growth conditions on the nature of optical excitations and fostering emerging optoelectronic applications of monolayer TMDs.