Synergetic Dopant and Additive Engineering of Hole Transporter for Outdoor‐Stable Perovskite Solar Modules

Abstract

ABSTRACT The spiro‐OMeTAD hole‐transport layer (HTL) underpins high‐performance n–i–p perovskite solar cells (PSCs), but conventional hygroscopic lithium dopants and volatile additives undermine operational stability and complicate module fabrication. Here we introduce a synergistic dopant–additive strategy that replaces both with a thermally stable Zn salt and vinylene carbonate (VC). The Zn:VC combination oxidizes spiro‐OMeTAD without air, promotes p‑radical formation, and raises the HTL glass‐transition temperature above 150°C. Consequently, we achieved a power conversion efficiency (PCE) of 26.3% for unit cells (0.16 cm 2 ) and 24.4% (23.96% certified) for modules (11.5 cm 2 )—among the highest reported for n–i–p perovskite modules. Modules retain 90% of initial efficiency after 2000 h damp‑heat exposure, 96% after 2500 h maximum‑power‑point tracking, and exhibit stable output over 30 days outdoor, demonstrating markedly improved operational robustness.