Intra- and interchain luminescence in amorphous and semicrystalline films of phenyl-substituted polythiophene

We report time-resolved photoluminescence (PL) measurements of spin-cast amorphous films of a regioregular polythiophene derivative poly[3-(4-octylphenyl)thiophene] and of annealed semicrystalline films of the same polymer with an interchain stacking distance of 5 Angstrom. Red-shifted PL appears at long delay times in both pristine and annealed films, which we assign to interchain aggregates populated by excitation energy migration. Aggregate luminescence in annealed films exhibits a pronounced vibronic structure indicating the coupling to a C=C bond stretch with a Huang-Rhys factor S = 2. Two types of aggregates are distinguished in annealed films: in a few picoseconds most excitations are trapped by aggregates with a large energy gap (about 1.83 eV) between the lowest excited singlet state and the ground state. Excitation energy is transferred or the aggregates relax structurally with a time constant of about 200 ps to aggregates with a smaller energy gap (about 1.75 eV). The radiative lifetime of aggregates with smaller energy gap is estimated to be about 35 ns, two times longer than that of aggregates with the larger energy gap. In spin-cast amorphous films, emission from intrachain singlet excitons has a longer lifetime than in annealed films and only high-energy-gap aggregates are populated.