Yu Zhong1 Baorui Cheng1 Chibeom Park1 Ariana Ray2 Sarah Brown1 Fauzia Mujid1 Jae-Ung Lee1 Hua Zhou3 Joonki Suh1 Kan-Heng Lee1 Andrew Mannix1 Kibum Kang4 Steven Sibener1 David Muller2 Jiwoong Park1

1, University of Chicago, Chicago, Illinois, United States
2, Cornell University, Ithaca, New York, United States
3, Argonne National Laboratory, Chicago, Illinois, United States
4, Korea Advanced Institute of Science and Technology, Daejeon, , Korea (the Republic of)

Two-dimensional (2D) materials own many interesting properties due to their atom-thick characteristics and versatile heterostructures built layer-by-layer. The capability of assembling both organic and inorganic 2D materials into heterostructures will lead to the formation of artificial van der Waals solids that takes advantage of molecular functionalities brought by the organic 2D materials. Towards this end, the biggest hurdle has been the lack of a general method to synthesize organic monolayers at macroscopic dimensions and integrate them with monolayer precision. Herein, we report the general synthesis of monolayer 2D polymers, the molecular analogs of 2D atomic crystals, with wafer-scale homogeneity and the fabrication of the hybrid superlattices. For this, we develop a new interfacial synthesis technique compatible with various molecular building blocks and polymerization chemistries. This approach incorporates key features necessary for scalable and facile processing, including large-area synthesis, ambient growth conditions, and compatibility with established patterning and integration methods. Enabled by those characteristics, hybrid organic-inorganic superlattices of monolayer 2D polymers and 2D atomic crystals were fabricated with molecular precision. The employment of versatile 2D polymers allows the incorporation of functional molecular moieties into two-dimensional electronic circuits. These materials show promising applications in multifunctional 2D electronic devices.