Two-dimensional (2D) covalent organic frameworks (COFs) with periodic functional n-electron systems are an emerging class of optoelectronic materials. However, almost all conjugated COFs so far are insoluble and hard to process, which hampers severely their optoelectronic applications. Here, a solution-processable, nanoscale and sp² carbon-conjugated COF-like material, PDPP-C20 was successfully designed and synthesized. The solution-processed PDPP-C20 films exhibit high crystallinity and excellent charge transport properties along out-of-plane directions, combined with the highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels of −5.36/−3.75 eV, making PDPP-C20 suitable for electronic device applications. An efficiency as high as 21.92% has been demonstrated when it was used as a functional interfacial layer in perovskite solar cells, coupled with dramatically improved stability in comparison with the control device due to the superior hydrophobicity of PDPP-C20 layer as well as its passivation effect on perovskite surface. Furthermore, the soluble PDPP-C20 could also be used as donor in bulk-heterojunction organic solar cells and an initial efficiency of 2.46% has been achieved. These results indicate that this new class of soluble and nanoscale COF-like materials should offer a new arena of functional materials for optoelectronic devices.

具有周期性功能性n电子系统的二维（2D）共价有机骨架（COF）是一类新兴的光电材料。但是，到目前为止，几乎所有共轭COF都是不溶的且难以加工，这严重阻碍了其光电应用。在这里，可溶液处理，纳米级和sp ²成功地设计合成了碳共轭类COF材料PDPP-C20。固溶处理的PDPP-C20薄膜具有高结晶度和沿面外方向的优异电荷传输性能，结合最高的分子轨道（HOMO）/最低的未占据分子轨道（LUMO）的水平为-5.36 / -3.75 eV ，使PDPP-C20适用于电子设备应用。当它用作钙钛矿太阳能电池的功能性界面层时，已证明其效率高达21.92％，由于PDPP-C20层的优异疏水性及其钝化作用，与控制装置相比，其稳定性大大提高。对钙钛矿表面的影响。此外，可溶性PDPP-C20还可以用作体异质结有机太阳能电池的施主，初始效率已达到2.46％。这些结果表明，这类新型的可溶性和纳米级的类似于COF的材料应该为光电子器件提供功能材料的新舞台。