Incorporating the intriguing covalent organic framework (COF) into devices and performing their advanced electronic nature are still challenging. Herein, we demonstrate the direct growth of 2D full-conjugated COF ultrathin films on dielectric hexagonal boron nitride (hBN) for the first time and study the carrier transporting characteristics of π-conjugated COF films. Under the optimized solvothermal conditions, few-layered COF-366 films with the covalent connection of tetra(p-aminophenyl)porphyrin and terephthaladehyde are selectively fabricated on mechanically exfoliated hBN flakes. COF-366 films on hBN substrate present red-shift absorption edge and decreased band gap compared to the bulk COF powders.The organic field-effect transistor device based on COF-366 ultrathin films demonstrates p-type current modulation with an On/Off ratio of 10 5 and mobility of 0.015 cm 2 V -1 s -1 . The present work represents a universal method for COF film growth on dielectric surface, and also provides important insight to the carrier transport of 2D π-conjugated system and potential applications of 2D COFs in electronics.
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