Packing Dependent Electronic Coupling in Single Poly(3-hexylthiophene) H- and J‑Aggregate Nanofibers

Nanofibers (NFs) of the prototype conjugated polymer, poly­(3-hexylthiophene) (P3HT), displaying H- and J-aggregate character are studied using temperature- and pressure-dependent photoluminescence (PL) spectroscopy. Single J-aggregate NF spectra show a decrease of the 0–0/0–1 vibronic intensity ratio from ∼2.0 at 300 K to ∼1.3 at 4 K. Temperature-dependent PL line shape parameters (i.e., 0–0 energies and 0–0/0–1 intensity ratios) undergo an abrupt change in the range of ∼110130 K suggesting a change in NF chain packing. Pressure-dependent PL lifetimes also show increased contributions from an instrument-limited decay component which is attributed to greater torsional disorder of the P3HT backbone upon decreasing NF volume. It is proposed that the P3HT alkyl side groups change their packing arrangement from a type I to type II configuration causing a decrease in J-aggregate character (lower intrachain order) in both temperature- and pressure-dependent PL spectra. Chain packing dependent exciton and polaron relaxation and recombination dynamics in NF aggregates are next studied using transient absorption spectroscopy (TAS). TAS data reveal faster polaron recombination dynamics in H-type P3HT NFs indicative of interchain delocalization whereas J-type NFs exhibit delayed recombination suggesting that polarons (in addition to excitons) are more delocalized along individual chains. Both time-resolved and steady-state spectra confirm that excitons and polarons in J-type NFs are predominantly intrachain in nature that can acquire interchain character with small structural (chain packing) perturbations