The effects of the incorporation of semiconducting single‐walled nanotubes (sc‐SWNTs) with high purity on the bulk heterojunction (BHJ) organic solar cell (OSC) based on regioregular poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (rr‐P3HT:PCBM) are reported for the first time. The sc‐SWNTs induce the organization of the polymer phase, which is evident from the increase in crystallite size, the red‐shifted absorption characteristics and the enhanced hole mobility. By incorporating sc‐SWNTs, OSC with a power conversion efficiency (PCE) as high as 4% can be achieved, which is ≈8% higher than our best control device. A novel application of sc‐SWNTs in improving the thermal stability of BHJ OSCs is also demonstrated. After heating at 150 °C for 9 h, it is observed that the thermal stability of rr‐P3HT:PCBM devices improves by more than fivefold with inclusion of sc‐SWNTs. The thermal stability enhancement is attributed to a more suppressed phase separation, as shown by the remarkable decrease in the formation of sizeable crystals, which in turn can be the outcome of a more controlled crystallization of the blend materials on the nanotubes.
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