Perovskite solar cells (PSCs) have rapidly emerged as one of the most promising photovoltaic technologies, achieving power conversion efficiencies (PCEs) exceeding 26% within just a decade. However, despite these impressive advancements, their long-term stability remains a critical challenge, as perovskite materials inherently suffer from intrinsic defects both in the bulk and at the surfaces of their polycrystalline films. These defects act as non-radiative recombination centers and contribute to ion migration, phase instability, and environmental degradation, collectively hindering long-term operational stability and posing challenges for large-scale fabrication.¹ To date, various passivation molecules have been reported to interact with charged defects in perovskites, leading to significant improvements in device performance; however, most of these molecules target only a single type of defect. Phthalocyanines (Pcs), planar aromatic macrocycles and p-type semiconductors, are well known as efficient hole-transporting materials (HTMs). ² While most studies on Pcs in PSCs have focused on their role as HTM alternatives to spiro-OMeTAD—achieving impressive efficiency and stability—their exceptional photophysical properties, charge-transport capabilities, and highly tunable chemical structures have increasingly encouraged their use as functional additives to control perovskite film crystallization, reduce defect densities, and enhance charge transport and extraction.³

In this work, we present a series of Pc-based passivating agents with rationally designed cations and anions, including pseudo-halides PF₆⁻, BF₄⁻, TFSI⁻, and iodide (I⁻), to reduce defect densities, suppress ion migration, improve crystallinity, and enhance carrier transport in perovskite films.⁴ Beyond the π-conjugated framework of the Pc macrocycle, which facilitates charge transport, ammonium and/or imidazolium cations with long alkyl chains can effectively occupy A-site vacancies (i.e., MA⁺), while the corresponding anions can passivate I⁻ vacancies and Pb–I antisite defects. This dual passivation strategy simultaneously enhances photovoltaic performance and device stability. These derivatives were employed as additives in the perovskite precursor solution at various concentrations. At an optimized concentration of 1 mmol%, the ZnPc-BF₄ derivative achieved the highest PCE of 22%, while all ZnPc-based additives significantly improved long-term device stability.