Efficient and ultrafast formation of long-lived charge-transfer exciton state in atomically thin cadmium selenide/cadmium telluride type-II heteronanosheets

Colloidal cadmium chalcogenide nanosheets with atomically precise thickness of a few atomic layers and size of 10-100 nm are two-dimensional (2D) quantum well materials with strong and precise quantum confinement in the thickness direction. Despite their many advantageous properties, excitons in these and other 2D metal chalcogenide materials are short-lived due to large radiative and nonradiative recombination rates, hindering their applications as light harvesting and charge separation/transport materials for solar energy conversion. We showed that these problems could be overcome in type-II CdSe/CdTe core/crown heteronanosheets (with CdTe crown laterally extending on the CdSe nanosheet core). Photoluminesence excitation measurement revealed that nearly all excitons generated in the CdSe and CdTe domains localized to the CdSe/CdTe interface to form long-lived charge transfer excitons (with electrons in the CdSe domain and hole in the CdTe domain). By ultrafast transient absorption spectroscopy, we showed that the efficient exciton localization efficiency could be attributed to ultrafast exciton localization (0.64 ± 0.07 ps), which was facilitated by large in-plane exciton mobility in these 2D materials and competed effectively with exiton trapping at the CdSe or CdTe domains. The spatial separation of electrons and holes across the CdSe/CdTe heterojunction effectively suppressed radiative and nonradiative recombination processes, leading to a long-lived charge transfer exciton state with a half-life of ∼ 41.7 ± 2.5 ns, ∼ 30 times longer than core-only CdSe nanosheets.