Despite the recent progress in the synthesis of crystalline boronate ester covalent organic frameworks (BECOFs) in powder and thin-film through solvothermal method and on-solid-surface synthesis, respectively, their applications in electronics, remain less explored due to the challenges in thin-film processability and device integration associated with the control of film thickness, layer orientation, stability and crystallinity. Moreover, although the crystalline domain sizes of the powder samples can reach micrometer scale (up to ≈1.5 μm), the reported thin-film samples have so far rather small crystalline domains up to 100 nm. Here we demonstrate a general and efficient synthesis of crystalline two-dimensional (2D) BECOF films composed of porphyrin macrocycles and phenyl or naphthyl linkers (named as 2D BECOF-PP or 2D BECOF-PN) by employing a surfactant-monolayer-assisted interfacial synthesis (SMAIS) on the water surface. The achieved 2D BECOF-PP is featured as free-standing thin film with large single-crystalline domains up to ≈60 μm2 and tunable thickness from 6 to 16 nm. A hybrid memory device composed of 2D BECOF-PP film on silicon nanowire-based field-effect transistor is demonstrated as a bio-inspired system to mimic neuronal synapses, displaying a learning–erasing–forgetting memory process.
Bibliographical noteFunding Information:
This work was financially supported by Graphene Flagship (Core 3), ERC Grants on T2DCP and FC2DMOF (grant agreement No. 852909) and COORNET (SPP 1928) as well as the German Science Council and Centre of Advancing Electronics Dresden, EXC1056, (cfaed). This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement 785219. We gratefully acknowledge the International Excellence Graduate School on Emerging Materials and Processes Korea (iEGSEMP Korea) in the context of TU Dresden Institutional Strategy The Synergetic University. We thank Dresden Center for Nanoanalysis (DCN) at TUD and Dr. Petr Formanek (IPF, Dresden) for the use of facilities.
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