Operando Direct Observation of Charge Accumulation and the Correlation with Performance Deterioration in PTB7 Polymer Solar Cells

Polymer solar cells are one of the promising energy sources because of the easy solution-processable production with large area at a low cost without toxicity. Among the polymer materials, a donor–acceptor conjugated copolymer PTB7 has been extensively studied because of the typical high-performance polymer solar cells. Here, we show operando direct observation of charge accumulation in PTB7:PC71BM blend solar cells from a microscopic viewpoint using electron spin resonance spectroscopy. The accumulation of ambipolar charges in the PTB7-based cells is directly observed for the first time, which shows a clear correlation with the performance deterioration during device operation. The sites of the ambipolar charge accumulation are elucidated at the molecular level, whose information would be useful for improving the cell durability in addition to the performance improvement.