Due to low glass-transition temperature and high diffusion coefficient of small molecule acceptors (SMAs), the bi-continuous interpenetrating morphology of SMA-based polymer solar cells (PSCs) are metastable and therefore most SMA-based PSCs exhibit poor operational and thermal stability. Cross-linked donor polymers have been proposed because the cross-linked behavior can “freeze” the initial morphology and avoid its further evolution. In this work, two new cross-linked donor polymers P1 and P2 were designed for application in PSCs with a non-fullerene acceptor Y6, in which the photovoltaic performance and thermal stability of PSCs were significantly improved. The P1-based PSCs achieved a superior power conversion efficiency (PCE) of 17.29 % with a Jsc of 25.99 mA cm−2, a Voc of 0.860 V and a FF of 77.35 %, which surpassed 9 % for PM6-based PSCs (15.86 %). Furthermore, the P1-based PSCs exhibited better thermal stability with a 17 % efficiency loss under continuous 60 °C for 210 h due to the fixation of active layer morphology, while PM6-based PSCs suffered from a serve PCE reduction of over 26 %. These results demonstrate that cross-linked donor polymer has a great application prospect to improve the PCE and thermal stability of PSCs.
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