Molar Mass versus Polymer Solar Cell Performance: Highlighting the Role of Homocouplings

Although a strong link between the molar mass of conjugated polymers and the performance of the resulting polymer:fullerene bulk heterojunction organic solar cells has been established on numerous occasions, a clear understanding of the origin of this connection is still lacking. Moreover, the usual description of molar mass and polydispersity does not include the shape of the polymer distribution, although this can have a significant effect on the device properties. In this work, the effect of molar mass distribution on photovoltaic performance is investigated using a combination of structural and electro-optical techniques for the state-of-the-art low bandgap copolymer PTB7. Some of the studied commercial PTB7 batches exhibit a bimodal distribution, of which the low molar mass fraction contains multiple homocoupled oligomer species, as identified by MALDI-TOF analysis. This combination of low molar mass and homocoupling drastically reduces device performance, from 7.0 to 2.7%. High molar mass batches show improved charge carrier transport and extraction with much lower apparent recombination orders, as well as a more homogeneous surface morphology. These results emphasize the important effect of molar mass distributions and homocoupling defects on the operation of conjugated polymers in photovoltaic devices.