A Polymeric Hole Transporter with Dual‐Interfacial Interactions Enables 25%‐Efficiency Blade‐Coated Perovskite Solar Cells

Abstract Self‐assembly monolayer (SAM) hole transporters, consisting of anchoring, spacer, and terminal groups, have played a significant role in the development of inverted perovskite solar cells (PSCs). However, the weak interaction between perovskite and hydrophobic terminal group of SAMs limits surface wettability and interface stability. To address this issue, two novel hole transporters (named DBPP and Poly‐DBPP) with centrosymmetric biphosphonic acid groups are developed. Unlike conventional SAM hole transporters, the biphosphonic acid groups in DBPP and Poly‐DBPP can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously, improving surface wettability and suppressing interface recombination. Furthermore, compared to the small‐molecular DBPP, Poly‐DBPP exhibits higher conductance and excellent uniformity. This translates to a remarkable power conversion efficiency of 25.1% for blade‐coated PSCs and 22.0% for large‐area modules, respectively. Additionally, the PSCs based on Poly‐DBPP demonstrate impressive operational stability, retaining 92% of their initial PCE after 1,600 h of light soaking. This work presents a promising strategy for designing multifunctional hole transporters, paving the way for highly efficient and stable PSCs.