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We fabricated P(NDI2OD-T2)/PTB7 bilayer all-polymer solar cells with an inverted configuration, where the annealing temperature was systematically varied. The current density–voltage behavior was investigated and the structuralproperties of the P(NDI2OD-T2) layers were characterized. Absorption spectroscopy, surface morphology, and crystallite analysis showed that increasing phase segregation of P(NDI2OD-T2) films occurred as the annealing temperature increased. We found that, as the P(NDI2OD-T2) stacking improved, with larger domains, the open-circuit voltage decreased and the saturation dark current density increased. This work provides a guide for the processing of P(NDI2OD-T2) layers to maximize the power conversion efficiency of all-polymer solar cells.


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