Formamidinium Lead Iodide‐Based Inverted Perovskite Solar Cells with Efficiency over 25 % Enabled by An Amphiphilic Molecular Hole‐Transporter

Abstract Formamidinium lead iodide (FAPbI 3 ) represents an optimal absorber material in perovskite solar cells (PSCs), while the application of FAPbI 3 in inverted‐structured PSCs has yet to be successful, mainly owing to its inferior film‐forming on hydrophobic or defective hole‐transporting substrates. Herein, we report a substantial improvement of FAPbI 3 ‐based inverted PSCs, which is realized by a multifunctional amphiphilic molecular hole‐transporter, (2‐(4‐(10 H ‐phenothiazin‐10‐yl)phenyl)‐1‐cyanovinyl)phosphonic acid (PTZ−CPA). The phenothiazine (PTZ) based PTZ−CPA, carrying a cyanovinyl phosphonic acid (CPA) group, forms a superwetting hole‐selective underlayer that enables facile deposition of high‐quality FAPbI 3 thin films. Compared to a previously established carbazole‐based hole‐selective material (2‐(3,6‐dimethoxy‐9 H ‐carbazol‐9‐yl)ethyl)phosphonic acid (MeO−2PACz), the crystallinity of FAPbI 3 is enhanced and the electronic defects are passivated by the PTZ−CPA more effectively, resulting in remarkable increases in photoluminescence quantum yield (four‐fold) and Shockley‐Read‐Hall lifetime (eight‐fold). Moreover, the PTZ−CPA shows a larger molecular dipole moment and improved energy level alignment with FAPbI 3 , benefiting the interfacial hole‐collection. Consequently, FAPbI 3 ‐based inverted PSCs achieve an unprecedented efficiency of 25.35 % under simulated air mass 1.5 (AM1.5) sunlight. The PTZ−CPA based device shows commendable long‐term stability, maintaining over 90 % of its initial efficiency after continuous operation at 40 °C for 2000 hours.