Discerning Bulk and Interfacial Polarons in a Dual Electron Donor/Acceptor Polymer

[Image: see text] The active layer of organic solar cells typically possesses a complex morphology, with amorphous donor/acceptor mixed domains present in addition to purer, more crystalline domains. These crystalline domains may represent an energy sink for free charges that aids charge separation and suppresses bimolecular recombination. The first step in exploiting this behavior is the identification and characterization of charges located in these different domains. Herein, the generation and recombination of both bulk and interfacial polarons are demonstrated in the dual electron donor/acceptor polymer XIND using transient absorption spectroscopy. The absorption spectra of XIND bulk polarons, present in pristine polymer domains, are clearly distinguishable from those of polarons present at the donor/acceptor interface. Furthermore, it is shown that photogenerated polarons are transferred from the interface to the bulk. These findings support the energy sink hypothesis and offer a way to maximize morphology relationships to enhance charge generation and suppress recombination.