Despite the huge progress achieved in the optimization of perovskite solar cell (PSC) performance, stability remains a limiting factor for technological commercialization. Here, a study on the photovoltaic, structural and morphological stability of semi-transparent formamidinium lead bromide-based PSCs is presented. This work focuses on the positive role of 2D nanoscale layer passivation, induced by perovskite surface treatment with a mixture of iso-Pentylammonium chloride (ISO) and neo-Pentylammonium chloride (NEO). In situ X-ray diffraction (XRD) is applied in combination with atomic force microscopy (AFM), and the results are correlated to the devices' photovoltaic performances. The superior power conversion efficiency and overall stability of the ISO-NEO system is evidenced, as compared to the un-passivated device, under illumination in air. Furthermore, the role of the ISO-NEO treatments in increasing the morpho-structural stability is clarified as follows: a bulk effect resulting in a protective role against the loss in crystallinity of the perovskite 3D phase (observed only for the un-passivated device) and an interface effect, being the observed 2D phase crystallinity loss spatially localized at the interface with the 3D phase where a higher concentration of defects is expected. Importantly, the complete stability of the device is achieved with the passivated ISO-NEO-encapsulated device, allowing us to exclude the intrinsic degradation effects.