During the past decade, the power conversion efficiency (PCE) of perovskite solar cells (PSCs) has risen rapidly, and it now approaches the record for single crystal silicon solar cells. However, these devices still suffer from a problem of stability. To improve PSC stability, two approaches have been notably developed: the use of additives and/or post-treatments that can strengthen perovskite structures and the use of a nontypical architecture where three mesoporous layers, including a porous carbon backcontact without hole transporting layer, are employed. This paper focuses on 5-ammonium valeric acid iodide (5-AVAI or AVA) as an additive in methylammonium lead iodide (MAPI). By combining scanning electron microscopy (SEM), X-ray diffraction (XRD), time-resolved photoluminescence (TRPL), current–voltage measurements, ideality factor determination, and in-depth electrical impedance spectroscopy (EIS) investigations on various layers stacks structures, we discriminated the effects of a mesoscopic scaffold and an AVA additive. The AVA additive was found to decrease the bulk defects in perovskite (PVK) and boost the PVK resistance to moisture. The triple mesoporous structure was detrimental for the defects, but it improved the stability against humidity. On standard architecture, the PCE is 16.9% with the AVA additive instead of 18.1% for the control. A high stability of TiO2
/carbon/perovskite cells was found due to both AVA and the protection by the all-inorganic scaffold. These cells achieved a PCE of 14.4% in the present work.
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