Multi-phase microstructures drive exciton dissociation in neat semicrystalline polymeric semiconductors

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure and phase morphology. Hence, it is of central importance to manipulate - from the outset - the molecular arrangement and packing of this special class of polymers from the nano- to the micrometer scale when they are integrated in thin film devices such as photovoltaic cells, transistors or light-emitting diodes, for example. One effective strategy for this purpose is to vary their molecular weight. The reason for this is that materials of different weight-average molecular weight (M_w) lead to different microstructures. Polymers of low M_w form unconnected, extended-chain crystals because of their non-entangled nature. As a result, a polycrystalline, one-phase morphology is obtained. In contrast, high-M_w materials, in which average chain lengths are longer than the length between entanglements, form two-phase morphologies comprised of crystalline moieties embedded in largely un-ordered (amorphous) regions. Here, we discuss how changes in these structural features affect exciton dissociation processes. We utilise neat regioregular poly(3-hexylthiophene) (P3HT) of varying M_w as a model system and apply time-resolved photoluminescence (PL) spectroscopy to probe the electronic landscape in a range of P3HT thin-film architectures. We find that at 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Tellingly, both the amplitude and decay-rate distribution depend strongly on M_w. In films with dominant one-phase, chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges. Its decay is significantly slower than in two-phase microstructures. We therefore conclude that excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure, in agreement with previous work [Paquin et al., Phys. Rev. Lett., 2011, 106, 197401]. We note, however, that independent of M_w, the delayed-PL lineshape due to charge recombination is representative of that in low-M_w microstructures. We thus hypothesize that charge recombination at these low temperatures - and likely also charge generation - occur in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, producing a delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state.