The development of stable and efficient hole-transporting materials (HTMs) is critical for the commercialization of perovskite solar cells (PSCs). Herein, a novel spiro-type HTM was designed and synthesized where N-ethylcarbazole-terminated groups fully substituted the methoxy group of spiro-OMeTAD, named spiro-carbazole. The developed molecule exhibited a lower highest occupied molecular orbital level, higher hole mobility, and extremely high glass transition temperature (T g = 196 °C) compared with spiro-OMeTAD. PSCs with the developed molecule exhibited a champion power conversion efficiency (PCE) of 22.01 %, which surpassed traditional spiro-OMeTAD (21.12 %). Importantly, the spiro-carbazole-based device had dramatically better thermal, humid, and long-term stability than spiro-OMeTAD.
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