C1jm12677f 15224..15231

Bulk heterojunction organic solar cells hold much promise as commercially viable sources of renewable energy due to their relatively inexpensive fabrication. Developing a fundamental knowledge of how processing conditions influence solar power conversion efficiency will enable rational and efficient design, optimization, and control of new organic solar cell materials. In this report, we use a combination of in situ current–voltage measurements and grazing-incidence wide-angle X-ray scattering experiments at elevated temperature to correlate the changes in photoconversion efficiency to the changes in the molecular ordering of a poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction active layer. In situ measurements of current–voltage characteristics were used to optimize the power conversion efficiency and the resulting thermal processing was in agreement with studies from repeated heating and cooling cycles. The improvements in short circuit current with thermal annealing were correlated to an increase in the population of faceon oriented crystallites of P3HT rather than improvements in molecular ordering of PCBM.