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The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of p-i-n PSCs. Specifically, ETMs based on three SubPcs (with either six or twelve peripheral fluorine and chlorine atoms) have been incorporated into PSCs with the perovskite layer deposited by solution processing (CsFAMAPbIBr). The device performance and morphology of these devices are deeply analyzed using several techniques, and the interfacial effects induced by the SubPcs are studied using photoluminescence and TR-PL. It is observed that the device stability is significantly improved upon insertion the SubPc layer. Moreover, the impact of the SubPc layer-thickness is assessed. Thus, a maximum power conversion efficiency of 13.6% was achieved with the champion device.

Due to their strong acceptor properties and enhanced charge transport capabilities, non-fullerene electron acceptors based on [Formula: see text]-extended derivatives – subnaphthalocyanines (SubNc) or subphtalocyanine dimers (SubPc[Formula: see text] – have been employed in organic photovoltaics in the past as an alternative to the expensive fullerene. However, these promising [Formula: see text]-extended derivatives have not been explored in perovskite solar cell technology. In this work, we implement a vacuum-deposited very thin film of SubNc or SubPc2 as electron transport layers in perovskite solar cells. In particular, we demonstrate the excellent electron extraction properties of the thin films in contact with perovskite layer. The fabricated perovskite solar cells exhibit enhanced device performances with reduced hysteresis index and improved device stability. Our results validate the use of [Formula: see text]-extended subporphyrinoids as promising candidates for perovskite optoelectronics with enhanced stability properties, being essential for further commercialization of the perovskite technology.

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