Designing a Length‐Modulated Azide Photocrosslinker to Improve the Stretchability of Semiconducting Polymers

To impart high stretchability to semiconducting polymers, researchers have used a photocrosslinking approach based on the nitrene chemistry of an azide‐incorporated molecular additive. However, understanding of the molecular design of azide crosslinkers with respect to their effects on the electrical and mechanical properties of semiconducting polymer thin films is lacking. In this study, the effects of an azide photocrosslinker's molecular length and structure on the microstructural, electrical features, and stretchability of photocrosslinked conjugated polymer films is investigated. For a systematic comparison, a series of nitrene‐induced photocrosslinkers (n‐NIPSs) with different numbers of ethylene glycol repeating units (n = 1, 4, 8, 13) that bridge two tetrafluoro‐aryl azide end groups is synthesized. Two semicrystalline conjugated polymers and two nearly amorphous conjugated polymers are co‐processed with n‐NIPSs and crosslinked by brief exposure to UV light. It is found that, among the synthesized n‐NIPSs, the shortest one (1‐NIPS) is the most efficient in improving the stretchability of crosslinked indacenodithiophene‐benzothiadiazole films and that the improvement is achieved only with nearly amorphous polymers, not with semicrystalline conjugated polymers. On the basis of systematic studies, it is suggested that crosslinking density in amorphous regions is important in improving thin film stretchability. The length‐modulated nitrene‐induced photocrosslinkers (n‐NIPS) are prepared by controlling the number of ethylene glycol units. Among n‐NIPS, the shortest 1‐NIPS shows uniform morphology and optimized intermolecular interaction in crosslinked thin films of benchmark conjugated polymers. The crosslinked thin film with 1‐NIPS exhibits a much‐improved crack‐onset strain up to 100%, and excellent charge transport retention even at an 80% unidirectional tensile strain.