Theoretical and experimental study of low band gap polymers for organic solar cells.

A combined theoretical and experimental investigation of the electronic structure and optical properties of poly(3-hexylthiophene) (P3HT), poly[3-(4-octylphenyl)thiophene] (POPT) and poly[3-(4-octylphenoxy)thiophene] (POPOT) is reported. In comparison with P3HT, POPT and POPOT exhibit better stabilities and the presence of an oxygen atom and/or a phenyl ring in the side chains enhances conjugation. Quantum chemical calculations have been performed on oligomers of increasing chain length to establish the changes in the electronic and optical properties when going from P3HT to the new derivative POPOT. The knowledge of the structure of these polymers is of utmost importance in understanding their optical properties in different phases (solution and condensed phase). The calculations indicate that, in opposition to P3HT and POPT polymers where the introduction of alkyl chains and the pendant phenyl disturbs the planarity of the backbone of the conjugated segment, POPOT has a better degree of organization in both states: the conjugated chain remains planar even in the presence of the phenoxy groups. Finally, the exciton binding energy is evaluated for these polymers and allows us to conclude that the POPOT is a promising polymer for photovoltaic applications when compared to P3HT and POPT. This journal is © the Owner Societies 2012