Luminescence quenching by inter-chain aggregates in substituted polythiophenes

Abstract

Time-resolved photoluminescence spectra measured in solid films of two polythiophene derivatives with different chain packing allow to distinguish emission of intra-chain excitations from the luminescence of inter-chain aggregates. Aggregate luminescence is red shifted by about 0.1 eV relative to intra-chain emission and shows vibronic coupling to the CC bond stretch with the Huang–Rhys factor of S≈1.5, which is twice bigger than that of the intra-chain emission. Combining time resolved luminescence data with femtosecond transient absorption, we show that the dynamic quenching of the luminescence in films with dense chain packing is mainly due to excitation energy transfer to aggregates. The radiative lifetime of the lowest excited state of the aggregate with the optical gap of 1.84–1.9 eV is estimated to be about 20 ns. The aggregate contribution to the total luminescence in the polythiophene films with dense chain packing is about 50% and does not change significantly with temperature.