Energetics of excited states in the conjugated polymer poly(3-hexylthiophene)

There is an enormous potential in applying conjugated polymers in novel organic optoelectronic devices such as light-emitting diodes and solar cells. Although prototypes and first products exist, a comprehensive understanding of the fundamental processes and energetics involved during photoexcitation is still lacking and limits further device optimizations. Here we report on a unique analysis of the excited states involved in charge generation by photoexcitation. On the model system poly(3-hexylthiophene), we demonstrate the general applicability of our approach. From photoemission spectroscopy of occupied and unoccupied states, we determine the transport gap to 2.6 eV, which we show to be in agreement with the onset of photoconductivity by spectrally resolved photocurrent measurements. For photogenerated singlet exciton at the absorption edge, 0.7 eV of excess energy are required to overcome the binding energy; the intermediate charge-transfer state is situated only 0.3 eV above the singlet exciton. Our results give direct evidence of energy levels involved in the photogeneration and charge transport within conjugated polymers.