Here we review the recent strategies for developing organic and inorganic molecular materials for application as electron and hole transport layers and as additives to achieve high efficiency and stability perovskite solar cells.

Solution-processed organic-inorganic halide perovskites are currently established as the hottest area of interest in the world of photovoltaics, ensuring low manufacturing cost and high conversion efficiencies. Even though various fabrication/deposition approaches and device architectures have been tested, researchers quickly realized that the key for the excellent solar cell operation was the quality of the crystallization of the perovskite film, employed to assure efficient photogeneration of carriers, charge separation and transport of the separated carriers at the contacts. One of the most typical methods in chemistry to crystallize a material is anti-solvent precipitation. Indeed, this classical precipitation method worked really well for the growth of single crystals of perovskite. Fortunately, the method was also effective for the preparation of perovskite films by adopting an anti-solvent dripping technique during spin-coating the perovskite precursor solution on the substrate. With this, polycrystalline perovskite films with pure and stable crystal phases accompanied with excellent surface coverage were prepared, leading to highly reproducible efficiencies close to 22%. In this review, we discuss recent results on highly efficient solar cells, obtained by the anti-solvent dripping method, always in the presence of Lewis base adducts of lead(II) iodide. We present all the anti-solvents that can be used and what is the impact of them on device efficiencies. Finally, we analyze the critical challenges that currently limit the efficacy/reproducibility of this crystallization method and propose prospects for future directions.