The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure. For example, the molecular-weight distribution influences polymeric- semiconductor properties via diverse microstructures; polyme
rs of low weight-average molecular weight (Mw) form unconnected, extended-chain crystals, usually of a paraffinic structure. Because of the non-entangled nature of the relatively short-chain macromolecules, this leads to a polycrystalline, one-phase morphology. In contrast, with high-Mw materials, where average chain lengths are longer than the length between entanglements, two-phase morphologies, comprised of crystalline moieties embedded in largely unordered (amorphous) regions, are obtained. We investigate charge photogeneration processes in neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw by means of time-resolved photoluminescence (PL) spectroscopy. At 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Both the amplitude and decay rate distribution depend strongly on Mw. In films with dominant one-phase chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges, and its decay is significantly faster than in two-phase microstructures. However, independent of Mw, charge recombination regenerates singlet excitons in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, with delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. We conclude that highly delocalized excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure.
We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsicall
y at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character.
