Quantitative bimolecular recombination in organic photovoltaics through triplet exciton formation

Abstract

The nanoscale morphology and high charge densities in organic photovoltaics (OPVs) lead to a high rate of bimolecular encounters between spin-uncorrelated electrons and holes. This process can lead to the formation of low-energy triplet excitons on the donor polymer that decay nonradiatively and limit the device performance. We use time-resolved optical spectroscopy to characterize the effect of morphology through the use of solvent additives such as 1,8-octanedithiol (ODT) on triplet dynamics and charge recombination in blends of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]- dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] and [6,6]-phenyl-C 71-butyric acid methyl ester. This is an attractive OPV system since the extended absorption of the polymer into the near-infrared gives good coverage of the solar spectrum, but nevertheless, the internal quantum efficiency (IQE) has not been reported to be higher than ∼65% under short circuit conditions. We find that, without ODT, the IQE is 48% and 16% of excitations decay via bimolecular triplet formation. With ODT treatment, which improves crystallinity and carrier mobility, the IQE increases to 65%, but bimolecular triplet formation significantly increases and now accounts for all of the recombination (35% of charges). © 2014 American Chemical Society.