LAUSR

Further enhancing the operational lifetime of inverted‐structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole‐selective contacts at the illumination side plays a key role in operational stability. In this work, the self‐anchoring benzo[rst]pentaphene (SA‐BPP) is developed as a new type of hole‐selective contact toward long‐term operationally stable inverted PSCs. The SA‐BPP molecule with a graphene‐like conjugated structure shows a higher photostability and mobility than that of the frequently‐used triphenylamine and carbazole‐based hole‐selective molecules. Besides, the anchoring groups of SA‐BPP promote the formation of a large‐scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small‐sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA‐BPP contact. Also, the SA‐BPP‐based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1‐sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole‐selective contacts provides a promising strategy for further improving the PSC stability.