Unraveling the Contribution of Residual Monomer to the Emission Spectra of Poly(3-hexylthiophene) Aggregates: Implications for Identifying H- and J‑type Coupling

Poly­(3-hexylthiophene) (P3HT) is a well-studied benchmark system for semiconducting polymers used in optoelectronic devices. In these materials, aggregation can improve charge transport efficiency or enhance emission yields depending on the interchain packing. This may be inferred from the absorption and emission spectra when analyzed using exciton coupling models such as the well-known H- and J-coupling model of Kasha. The more recently developed weakly coupled H-aggregate (WCH) model quantifies the degree of disorder via the ratio of the electronic origin intensity to that of the first vibronic band. Here, the underlying assumptions of this approach are tested experimentally for P3HT aggregates formed by solvent poisoning using bulk and single-molecule-based spectroscopic techniques. Specifically, we show that the contribution of residual monomeric chains to the aggregate spectrum must be accounted for to properly assign the spectra as H- or J-type. A modification of the WCH model is introduced to account for multiple emissive species.