Spacer Regulation of the Novel Pyrene‐Based Tetrapodal Self‐Assembled Monolayers for Efficient and Stable Inverted Perovskite Solar Cells and Modules

Multipodal self‐assembled monolayers (SAMs) composed of π‐conjugated aromatic units have emerged as highly promising hole‐transporting layers in perovskite solar cells (PSCs) due to their excellent interfacial anchoring and scalable fabrication. However, it remains a formidable challenge to develop high‐performance tetrapodal SAMs that can simultaneously achieve ideal surface coverage, enhanced device efficiency, and improved long‐term stability. Herein, we rationally designed and synthesized two novel pyrene‐centered tetrapodal SAMs, 4PACz‐Py‐C2 and 4PACz‐Py‐C4. Spacer engineering has been employed to regulate molecular packing, facilitate hole extraction, and suppress non‐radiative recombination. The optimized PSCs based on 4PACz‐Py‐C2 achieved a power conversion efficiency (PCE) of 26.61% and maintained 90.1% of their initial PCE after 2000 h of maximum power point (MPP) tracking, demonstrating outstanding commercialization potential. Moreover, perovskite solar modules (aperture area: 21 cm 2 ) and 1.68 eV wide‐bandgap perovskite devices based on 4PACz‐Py‐C2 yielded high PCEs of 23.52% and 23.48%, respectively. This work exhibits significant application value in the development of novel multipodal SAMs for enhancing the efficiency and stability of PSCs.