Less Is More: Simplified Fluorene-Based Dopant-Free Hole Transport Materials Promote the Long-Term Ambient Stability of Perovskite Solar Cells

The stability of perovskite solar cells (PSCs) is greatly affected by the interface between the perovskite active layer and the hole transport material (HTM). The rational design of HTMs with effective anchoring to the perovskite surface is an emerging elegant strategy to promote compact and ordered interfaces that lead to highly efficient and stable PSCs. Herein, we propose two fluorene-based HTM molecular architectures (SCF1 and SCF2) derived from the popular yet expensive Spiro-OMeTAD. Their employment as dopant-free HTMs in standard triple-cation CsFAMA PSCs leads to superior device stability, with a T₈₀ lifetime well above 1 year (431 days). Our combined theoretical and experimental study of the CsFAMA|HTM interface reveals that the improved adhesion of the SCF-HTMs to the perovskite layer is the key to minimize the non-radiative recombination, reduce the hole trap density, and enhance the long-term stability of the corresponding devices. The simplified structures of SCF1 and SCF2, obtained by removing the orthogonal fragment of the Spiro-OMeTAD scaffold, show a lower molecular distortion than Spiro-OMeTAD, thus promoting a favorable electronic interaction between the SCF-HTMs and the perovskite. This study provides useful design criteria for achieving highly stable PSCs including dopant-free HTMs with optimized adhesion to the perovskite surface.