Revealing the Role of Polydispersity in Multilevel Assembly Structures and Its Correlation with the Mechanical and Electrical Properties of IDTBT Thin Films

Molecular weight optimization is crucial for high-performance stretchable conjugated polymer films. However, an in-depth understanding of molecular weight distribution on solution assembly, film microstructures, and electrical/mechanical properties of conjugated polymers is lacking. Herein, a model conjugated polymer, poly(indacenodithiophene-co-benzothiadiazole) (IDTBT), with a similar weight-average molecular weight but different polydispersity indexes (PDIs) of 3.2, 2.4, and 1.6 is investigated. The low-PDI polymer, containing a high content of homogeneous long chains, facilitates sufficient interchain aggregation caused by the enhanced chain entanglement and prolonged aggregation dynamics, which creates a low-crystallinity film containing long-chain well-connected aggregates and chain entanglement networks. Consequently, the charge mobility increases from 2.1 to 3.1 cm² V^–1 s^–1 as PDI decreases from 3.2 to 1.6. During stretching, the polymer chains align more effectively along the strain direction in the low-PDI film, which creates more dynamic sliding sites and short-range aggregates to dissipate the strain energy. Thus, the low-PDI polymer film exhibits a high charge mobility of 1.0 ± 0.1 cm² V^–1 s^–1 at 100% strain and 0.9 ± 0.1 cm² V^–1 s^–1 after 100 cycles of stretching–releasing at 25% strain, which significantly outperforms the high-PDI film. This work demonstrates the significance of polydispersity optimization for developing mechanically robust polymer semiconductor films in stretchable electronics.