Effect of Blend Composition and Additives on the Morphology of PCPDTBT:PC₇₁BM Thin Films for Organic Photovoltaics

The use of solvent additives in the fabrication of bulk heterojunction polymer:fullerene solar cells allows to boost efficiencies in several low bandgap polymeric systems. It is known that solvent additives tune the nanometer scale morphology of the bulk heterojunction. The full mechanism of efficiency improvement is, however, not completely understood. In this work, we investigate the influences of blend composition and the addition of 3 vol % 1,8-octanedithiol (ODT) as solvent additive on polymer crystallization and both, vertical and lateral morphologies of poly­[2,6-(4,4-bis­(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b′]­dithiophene)-<i>alt</i>-4,7­(2,1,3-benzothiadiazole)] and [6,6]-phenyl C₇₁-butyric acid methyl ester (PCPDTBT:PC₇₁BM) blend thin films processed from chlorobenzene-based solutions. The nanoscale morphology is probed with grazing incidence small- and wide-angle X-ray scattering as well as X-ray reflectivity and complemented with UV/vis spectroscopy. In PCPDTBT:PC₇₁BM films the use of ODT is found to lower the solubility of fullerene in the polymer matrix and to promote polymer crystallization, both vertical and lateral microphase separation with morphological coarsening, and formation of a fullerene-rich topping layer. The enhanced photovoltaic performance is explained by these findings