New synthetic strategies are ceaselessly being explored to fabricate covalent organic frameworks (COFs) as continuous materials with controlled morphology. However, making substrate detachable thin layers of 3D COFs, which would allow for film-based applications, has turned out to be particularly difficult. Here, we developed a substrate-catalyzed synthesis in a continuous flow method that successfully realized the fabrication of crystalline detachable all-carbon-linked 3D SBFdiyne-COF films. The key element in the method is a highly controlled interfacial reaction between the Cu substrate and a base flowing over the substrate. Benefiting from the detachability and high quality of the fabricated film, an organic semiconductor/COF heterojunction was constructed, showing high current rectification performance of 10⁴ under forward/reverse bias.

不断探索新的合成策略以将共价有机框架 (COF) 制造为具有受控形态的连续材料。然而，制造可分离的 3D COF 薄层，这将允许基于薄膜的应用，结果证明是特别困难的。在这里，我们开发了一种连续流动方法的底物催化合成，成功实现了结晶可分离全碳连接 3D SBFdiyne-COF 薄膜的制造。该方法的关键要素是铜基板和流过基板的基体之间高度可控的界面反应。受益于所制备薄膜的可分离性和高质量，构建了有机半导体/COF异质结，表现出10 ^{4的高电流整流性能}在正向/反向偏置下。