The Impact of Aggregation on the p-Doping Kinetics of Poly(3-hexylthiophene)

The morphological effects of regioregular poly(3-hexylthiophene) (P3HT) on its p-doping kinetics with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ) in solution are studied using optical absorption spectroscopy and stopped-flow technique. Two morphological forms, solubilized (s-P3HT) and nanowhiskers (nw-P3HT), are investigated. Both P3HT solubilized and aggregated solutions show similar characteristic near-IR absorption bands for integer charge transfer products with F₄-TCNQ. Kinetic analysis on p-doping of s-P3HT with F₄-TCNQ indicates that the doping reaction proceeds with a single reaction mechanism that is first order in s-P3HT. The doping kinetics of P3HT aggregate solution shows two distinctive reaction mechanisms. The slow mechanism has a reaction rate constant similar to that of solubilized P3HT solution, so it likely results from s-P3HT components that are present in the aggregate solution. The fast one is assigned to the nw-P3HT component, probably due to more efficient charge delocalization in the aggregated P3HT nanostructures. Additionally, the kinetic trends of the p-doping reactions are better fitted with the consideration of a Gaussian-like distribution of reactivities from P3HT, matching the complexity of polymeric systems originating from molecular weight and morphology variations. This study highlights the importance of considering different morphological forms of conjugated polymers on their charge-transfer reaction kinetics. The knowledge gained here should be fundamentally and practically important for future chemical doping applications in organic electronic device fabrications.