Organic solar cells based on D18:Y6 recently exhibited a record power conversion efficiency of over 18%. We have initially studied the molecular packing and thermodynamic properties of three D18:NFA blends by employing synchrotron X-ray techniques, secondary ion mass spectrometry and UV-vis miscibility measurements. The D18 polymer exhibits strong chain extension in films, which is beneficial to charge transport. Miscibility and other characterizations explain the disparate performance of three systems and the processing procedures. Our contribution reveals several unique property–performance relations of D18-based photovoltaic devices and help guide design or fabrication of yet higher efficiency organic solar cells.
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