Toward organic thin-film transistors: design, synthesis and application of covalent organic frameworks

Abstract Organic thin-film transistors (OTFTs) represent foundational components of flexible electronics, holding immense promises in flexible displays, wearable sensing, and low-cost optoelectronic detection. Nevertheless, their widespread implementation is currently constrained by the inherent environmental sensitivity of organic semiconductor active materials, leading to performance degradation, and the inability of conventional dielectric layers to meet high integration and thermal stability. Covalent organic frameworks (COFs), a novel class of crystalline porous polymers formed by robust covalent bonds, emerge as a compelling solution. Leveraging unique attributes—including precise pore tunability, high specific surface area, and long-range ordered π -conjugated systems—COFs offer a versatile materials platform to tackle key challenges in OTFTs. This review systematically summarizes the structure-property relationships and interface synthesis strategies of COFs, with a primary focus on their pivotal role as semiconductor active layers and dielectric materials in OTFTs. We delineate key design strategies and recent progress across diverse aspects, including molecular building blocks, linkage chemistry, topological structures, molecular symmetry, and thin-film integration. Finally, we provide an outlook on future directions of COF synthesis engineering, post-functionalization strategies, and physical-chemical mechanism studies to further advance this field.