%0 Journal Article %T Crystallization-Arrested Viscoelastic Phase Separation in Semiconducting Polymer Gels %J - %D 2019 %R https://doi.org/10.1021/acsapm.8b00195 %X Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) in ortho-dichlorobenzene formed thermoreversible gels. Confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation (VPS), which arrested prematurely during the formation of micron-sized solvent-rich ¡°holes¡± due to interchain crystallization. Cryogen-based scanning electron microscopy uncovered an interfibrillar network exhibiting nanosized pores. These networks formed to equal gel strengths when a third component, either small molecule phenyl-C61-butyric acid methyl ester or noncrystallizing regiorandom, poly(3-hexylthiophene), was added to the solution. Organic solar cells deposited with active layers from phase-separated solutions displayed 45% higher efficiency compared to reference cells. The demonstrated ability to arrest VPS enables control over the morphology of porous materials for applications ranging from membrane filtration to plastic foam manufacturing %U https://pubs.acs.org/doi/10.1021/acsapm.8b00195