Intrinsically Stretchable and Efficient Fully Π‐Conjugated Polymer via Internal Plasticization for Flexible Deep‐Blue Polymer Light‐Emitting Diodes with CIEy = 0.08

Intrinsically stretchable polymeric semiconductors are essential to flexible polymer light-emitting diodes (PLEDs) owing to their excellent strain tolerance capacity under long-time deformation operation. Obtaining intrinsic stretchability, robust emission properties, and excellent charge-transport behavior simultaneously from fully π-conjugated polymers (FCPs) is difficult, particularly for applications in deep-blue PLEDs. Herein, an internal plasticization strategy is proposed to introduce a phenyl-ester plasticizer into polyfluorenes (PF-MC4, PF-MC6, and PF-MC8) for narrowband deep-blue flexible PLEDs. Compared with controlled poly[4-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]-co-[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl] (PODPFs) (2.5%), the freestanding PF-MC8 thin film shows a fracture strain of >25%. The three stretchable films exhibit stable and efficient deep-blue emission (PLQY > 50%) because of the encapsulation of π-conjugated backbone via pendant phenyl-ester plasticizers. The PF-MC8-based PLEDs show deep-blue emission, which corresponds to CIE and EQE values of (0.16, 0.10) and 1.06%, respectively. Finally, the narrowband deep-blue electroluminescence (FWHM of ≈25 nm; CIE coordinates: (0.15, 0.08)) and performance of the transferred PLEDs based on the PF-MC8 stretchable film are independent of the tensile ratio (up to 45%); however, they show a maximum brightness of 1976 cd m^-2 at a ratio of 35%. Therefore, internal plasticization is a promising approach for designing intrinsically stretchable FCPs for flexible electronics.