Tuning Hole Transport Properties and Perovskite Crystallization via Pyridine‐Based Molecules for Quasi‐2D Perovskite Solar Cells

Abstract Quasi‐2D perovskites show great potential as photovoltaic devices with superior stability, but the power conversion efficiency (PCE) is limited by poor carrier transport. Here, it is simultaneously affected the hole transport layer (HTL) and the perovskite layer by incorporating pyridine‐based materials into poly(3,4‐ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) to address the key problem above in 2D perovskites. With this approach, the enhanced optoelectronic performance of the novel PEDOT:PSS is due to electron transfer between the additives and PEDOT or PSS, as well as a dissociation between PEDOT and PSS based on experimental and theoretical studies, which facilitates the charge extraction and transfer. Concurrently, in‐situ X‐ray scattering studies reveal that the introduction of pyridine‐based molecules alters the transformation process of the perovskite intermediate phase, which leads to a preferred orientation and ordered distribution caused by the Pb─N chemical bridge, achieving efficient charge transport. As a result, the pyridine‐treated devices achieve an increased short‐circuit current density ( J sc ) and PCE of over 17%.