Entanglement of Conjugated Polymer Chains Influences Molecular Self‐Assembly and Carrier Transport

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Abstract
The influence of polymer entanglement on the self‐assembly, molecular packing structure, and microstructure of low‐Mw (lightly entangled) and high‐Mw (highly entangled) poly (3‐hexylthiophene) (P3HT), and the carrier transport in thin‐film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self‐assembly of well‐ordered and highly textured fibrils at the solid–liquid interface. In low‐Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high‐Mw P3HT solutions increases carrier mobility up to ≈20‐fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high‐Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low‐Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport.

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