A Self‐Assembled Vertical‐Gradient and Well‐Dispersed MXene Structure for Flexible Large‐Area Perovskite Modules

Abstract Advancing hole transport layers (HTL) to realize large‐area, flexible, and high‐performance perovskite solar cells (PSCs) is one of the most challenging issues for its commercialization. Here, a self‐assembled gradient Ti₃C₂T_x MXene incorporated PEDOT:PSS HTL is demonstrated to achieve high‐performance large‐area PSCs by establishing half‐caramelization‐based glucose‐induced MXene redistribution. Through this process, the Ti₃C₂T_x MXene nanosheets are spontaneously dispersed and redistributed at the top region of HTL to form the unique gradient distribution structure composed of MXene:Glucose:PEDOT:PSS (MG‐PEDOT). These results show that the MG‐PEDOT HTL not only offers favorable energy level alignment and efficient charge extraction, but also improves the film quality of perovskite layer featuring enlarged grain size, lower trap density, and longer carrier lifetime. Consequently, the power conversion efficiency (PCE) of the flexible device based on MG‐PEDOT HTL is increased by 36% compared to that of pristine PEDOT:PSS HTL. Meanwhile, the flexible perovskite solar minimodule (15 cm² area) using MG‐PEDOT HTL achieve a PCE of 17.06%. The encapsulated modules show remarkable long‐term storage stability at 85 °C in ambient air (≈90% efficiency retention after 1200 h) and enhanced operational lifetime (≈90% efficiency retention after 200 h). This new approach shows a promising future of the self‐assembled HTLs for developing optoelectronic devices.