A diazirine‐based four‐armed cross‐linker (4CNN) with a tetrahedron geometry is presented for efficient patterning of polymeric semiconductors by photo‐induced carbene insertion. After blending of 4CNN with no more than 3 % (w/w), photo‐patterning of p‐, n‐, and ambipolar semiconducting polymers with side alkyl chains was achieved; regular patterns with size as small as 5 μm were prepared with appropriate photomasks after 365 nm irradiation for just 40 s. The interchain packing order and the thin film morphology were nearly unaltered after the cross‐linking and the semiconducting properties of the patterned thin films were mostly retained. A complementary‐like inverter with a gain value of 112 was constructed easily by two steps of photo‐patterning of the p‐type and n‐type semiconducting polymers. The results show that 4CNN is a new generation of cross‐linker for the photo‐patterning of polymeric semiconductors for all‐solution‐processible flexible electronic devices.

The soft nature has endowed conjugated polymers with promising applications in a wide range of field‐effect transistor (FET) based flexible electronics. With unremitting efforts on revealing the molecular structure–property relationships, numerous novel conjugated polymers with high mobility and excellent mechanical property have been developed in the past decades. Incorporating hydrogen‐bonding (H‐bonding) units into semiconducting polymers is one of the most successful strategies for designing high‐performance semiconducting materials. In this review, we aim to highlight the roles of H‐bonding units in the performances of polymeric FETs from three aspects. These include (i) charge mobility enhancement for semiconducting polymers after incorporation of H‐bonding units into the side chains, (ii) the effects of H‐bonding units on the stretchability of conjugated polymers, and (iii) the improvement of self‐healing properties of conjugated polymers containing dynamic hydrogen bonds due to the H‐bonding units in the side chains or conjugated backbones.