Molecular dynamics simulations of organohalide perovskite precursors: Solvent effects in the formation of perovskite solar cells

The stability and desirable crystal formation of organohalide perovskite semiconductors is of utmost relevance to ensure the success of perovskites in photovoltaic technology. Herein we have simulated the dynamics of ionic precursors toward the formation of embryonic organohalide perovskite CH₃NH₃PbI₃ units in the presence of solvent molecules using Molecular Dynamics. The calculations involved, a variable amount of Pb²⁺, I^-, and CH₃NH₃⁺ ionic precursors in water, pentane and a mixture of these two solvents. Suitable force fields for solvents and precursors have been tested and used to carry out the simulations. Radial distribution functions and mean square displacements confirm the formation of basic perovskite crystalline units in pure pentane - taken as a simple and archetypal organic solvent. In contrast, simulations in water confirm the stability of the solvated ionic precursors, which prevents their aggregation to form the perovskite compound. We have found that in the case of a water/pentane binary solvent, a relatively small amount of water did not hinder the perovskite formation. Thus, our findings suggest that the cause of the poor stability of perovskite films in the presence of moisture is a chemical reaction, rather than the polar nature of the solvents. Based on the results, a set of force-field parameters to study from first principles perovskite formation and stability, also in the solid phase, is proposed.