Electronically Coupled 2D Polymer/MoS2 Heterostructures

• Published in: Journal of the American Chemical Society Vol. 142; no. 50; pp. 21131 - 21139
• Main Authors: Balch, Halleh B, Evans, Austin M, Dasari, Raghunath R, Li, Hong, Li, Ruofan, Thomas, Simil, Wang, Danqing, Bisbey, Ryan P, Slicker, Kaitlin, Castano, Ioannina, Xun, Sangni, Jiang, Lili, Zhu, Chenhui, Gianneschi, Nathan, Ralph, Daniel C, Brédas, Jean-Luc, Marder, Seth R, Dichtel, William R, Wang, Feng
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16.12.2020; American Chemical Society (ACS)
• Subjects: Energy transfer; Heterostructures; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Layered materials; Layers; photoluminescence; semiconductors; Thin films; van der Waals forces
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.0c10151

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS2 heterostructures. Control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.