Clarifying the Dominant Role of Crystallinity and Molecular Orientation in Differently Processed Thin Films of Regioregular Poly(3-hexylthiophene)

Conjugated polymers (CPs) offer the potential for sustainable semiconductor devices due to their low cost and inherent molecular self-assembly. Enhanced crystallinity and molecular orientation in thin films of solution-processable CPs have significantly improved organic electronic device performance. In this work, three methods, namely spin coating, dip coating, and unidirectional floating-film transfer method (UFTM), were utilized with their parametric optimization for fabricating RR-P3HT films. These films were then utilized for their characterization via optical and microstructural analysis to elucidate dominant roles of molecular orientation and crystallinity in controlling charge transport in organic field-effect transistors (OFETs). OFETs fabricated by RR-P3HT thin films using spin coating and dip coating displayed field-effect mobility (μ) of 8.0 × 10−4 cm2V−1s−1 and 1.3 × 10−3 cm2V−1s−1, respectively. This two-time enhancement in µ for dip-coated films was attributed to its enhanced crystallinity. Interestingly, UFTM film-based OFETs demonstrated μ of 7.0 × 10−2 cm2V−1s−1, >100 times increment as compared to its spin-coated counterpart. This superior device performance is attributed to the synergistic influence of higher crystallinity and molecular orientation. Since the crystallinity of dip-coated and UFTM-thin films are similar, ~50 times improved µ of UFTM thin films, this suggests a dominant role of molecular orientation as compared to crystallinity in controlling the charge transport.