Band Structure Engineering of Interfacial Semiconductors Based on Atomically Thin Lead Iodide Crystals

To explore new constituents in two‐dimensional (2D) materials and to combine their best in van der Waals heterostructures is in great demand as being a unique platform to discover new physical phenomena and to design novel functionalities in interface‐based devices. Herein, PbI₂ crystals as thin as a few layers are synthesized, particularly through a facile low‐temperature solution approach with crystals of large size, regular shape, different thicknesses, and high yields. As a prototypical demonstration of band engineering of PbI₂‐based interfacial semiconductors, PbI₂ crystals are assembled with several transition metal dichalcogenide monolayers. The photoluminescence of MoS₂ is enhanced in MoS₂/PbI₂ stacks, while a dramatic photoluminescence quenching of WS₂ and WSe₂ is revealed in WS₂/PbI₂ and WSe₂/PbI₂ stacks. This is attributed to the effective heterojunction formation between PbI₂ and these monolayers; type I band alignment in MoS₂/PbI₂ stacks, where fast‐transferred charge carriers accumulate in MoS₂ with high emission efficiency, results in photoluminescence enhancement, and type II in WS₂/PbI₂ and WSe₂/PbI₂ stacks, with separated electrons and holes suitable for light harvesting, results in photoluminescence quenching. The results demonstrate that MoS₂, WS₂, and WSe₂ monolayers with similar electronic structures show completely distinct light–matter interactions when interfacing with PbI₂, providing unprecedented capabilities to engineer the device performance of 2D heterostructures.