In this work, electrodeposition was explored as an alternative technique for elaborating large-scale and homogeneous perovskite layers for photovoltaic application. This method was used to elaborate simple MAPbI 3 and mixed halide perovskites MAPbI 3−x Cl x . PbO 2 was first electrodeposited in a controlled manner. Next, the conversion into perovskite was conducted with various iodine/chlorine ratios. This produced different compositions of perovskites combining an interesting range of microstructural and functional properties. These perovskites, obtained for the first time using electrodeposition, were then tested in solar cell devices. The performances obtained with these innovative electrodeposited mixed perovskites are excellent, better than those obtained with most of the common forms of MAPbI 3 published so far. In addition, the stability of these electrodeposited perovskites has been evaluated under mild aging conditions (40 °C, under vacuum or an ambient atmosphere) for 500 h. For the treatment under vacuum, a maturation process was evidenced inducing an improvement of PCE close to 40%, to reach 7%. These results are of great interest, especially considering the active area tested close to 0.2 cm 2 . The addition of Cl in the lattice not only limits the formation of by-products (PbI 2 , MAPbCl 3 , etc.) and enhances the efficiency of the solar cells but also largely increases the stability.

The electrodeposition technique was explored as a powerful method for perovskite fabrication. It possesses the ability to elaborate high-quality perovskite layers on large-size substrates, with minimal manufacturing costs. In this work, the electrodeposition of PbO2 was conducted as a first step to elaborate MAPbI3 perovskite layers. Two conversion routes have been considered to reach the perovskite film. The first one is an immediate conversion of PbO2 into PK1 by immersion in methylammonium iodide (MAI, CH3NH3I) solution. The second route is a two-step conversion: initial PbO2 conversion into PbI2 by immersion in hydrogen iodide (HI), followed by PbI2 conversion into PK2 by immersion in MAI. For further evaluation of the impact of the conversion pathway and the nature of the substrate, an in-depth study of the microstructure, the morphology, and the key properties for the application of the perovskite layers has been conducted using a set of dedicated characterization techniques. Perovskite solar cells have also been developed using the electrodeposited active layers, which opens the way to promising performances using electrodeposition.