Ultrastable Supramolecular Self-Encapsulated Wide-Bandgap Conjugated Polymers for Large-Area and Flexible Electroluminescent Devices

Controlling chain behavior through smart molecular design provides the potential to develop ultrastable and efficient deep-blue light-emitting conjugated polymers (LCPs). Herein, a novel supramolecular self-encapsulation strategy is proposed to construct a robust ultrastable conjugated polydiarylfluorene (PHDPF-Cz) via precisely preventing excitons from interchain cross-transfer/coupling and contamination from external trace H₂O/O₂. PHDPF-Cz consists of a mainchain backbone where the diphenyl groups localize at the 9-position as steric bulk moieties, and carbazole (Cz) units localize at the 4-position as supramolecular π-stacked synthon with the dual functionalities of self-assembly capability and hole-transport facility. The synergistic effect of the steric bulk groups and π-stacked carbazoles affords PHDPF-Cz as an ultrastable property, including spectral, morphological stability, and storage stability. In addition, PHDPF-Cz spin-coated gelation films also show thickness-insensitive deep-blue emission with respect to the reference polymers, which are suitable to construct solution-processed large-scale optoelectronic devices with higher reproducibility. High-quality and uniform deep-blue emission is observed in large-area solution-processed films. The electroluminescence shows high-quality deep-blue intrachain emission with a CIE (0.16, 0.12) and a very narrow full width at half-maximum of 32 nm. Finally, large-area and flexible polymer light-emitting devices with a single-molecular excitonic behavior are also fabricated. The supramolecular self-encapsulation design provides an effective strategy to construct ultrastable LCPs for optoelectronic applications.