Organic solar cells (OSCs) are promising renewable energy sources for replacing fossil fuels. The power conversion efficiency (PCE) of OSCs has increased based on tremendous effort in material and device engineering. Still, the stability of OSC, such as long lifetime, negative temperature coefficient, must be enhanced for commercialization. In this study, we investigated OSC performance at a high operating temperature near 300–420 K, which are typical temperature regions in photovoltaic applications, with a different hole-extraction layer (HEL). The metal oxide-based HEL, MoO3, exhibited stable operating properties with a PCE drop rate of −0.13%/°C, as compared to polymeric HEL, PEDOT:PSS (−0.20%/°C). This performance reduction of polymeric HEL originated from the degradation of the interface in contact with PEDOT:PSS, as compared to the robust inorganic metal oxide HEL.

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