The domain size of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in the bulk heterojunction (BHJ) of organic photovoltaic (OPV) devices is of great importance to the performance and lifetime of a device. This study focuses on the use of polystyrene-tethered fullerenes (PTFs) as an additive to reduce the initial domain size of PCBM as well as to mitigate the growth of these domains over time that typically results in decreased device efficiency. Films were prepared from a 1:1 mixture of P3HT:PCBM on silicon wafers to approximate a BHJ system. PTFs were added in concentrations ranging from 0 to 20%. The samples were then annealed at 150 degrees C for varying times ranging from 5 to 60 min and examined by SEM to determine the average PCBM domain sizes for each sample. As expected, the control sample containing no additive showed significant growth in the PCBM domains as the sample was annealed with a final average domain size of 290 mu m(2). However, addition of as little as 5% PTFs produced average PCBM domain sizes after 60 min of annealing of 28 mu m(2). Addition of 20% PTF resulted in an average PCBM domain size of 2 mu m(2). Photoluminescence spectroscopy (PL) studies were performed on the films to study their electrical properties and based on these encouraging results; devices containing these architectures were prepared. OPVs with PTFs showed an increased lifetime, and in some cases, an increase in efficiency over devices containing no PTF. (C) 2013 Elsevier B.V. All rights reserved.