A combined molecular dynamics and experimental study of two-step process enabling low-temperature formation of phase-pure α-FAPbI3

It is well established that the lack of understanding the crystallization process in a two-step sequential deposition has a direct impact on efficiency, stability, and reproducibility of perovskite solar cells. Here, we try to understand the solid-solid phase transition occurring during the two-step sequential deposition of methylammonium lead iodide and formamidinium lead iodide. Using metadynamics, x-ray diffraction, and Raman spectroscopy, we reveal the microscopic details of this process. We find that the formation of perovskite proceeds through intermediate structures and report polymorphs found for methylammonium lead iodide and formamidinium lead iodide. From simulations, we discover a possible crystallization pathway for the highly efficient metastable alpha phase of formamidinium lead iodide. Guided by these simulations, we perform experiments that result in the low-temperature crystallization of phase-pure alpha-formamidinium lead iodide.

Automated summary

This study investigated the solid-solid phase transition during two-step sequential deposition, revealing microscopic details through metadynamics, x-ray diffraction, and Raman spectroscopy. Polymorphs were identified for methylammonium lead iodide and formamidinium lead iodide, with a possible crystallization pathway for the highly efficient metastable alpha phase of formamidinium lead iodide discovered through simulations. Experiments guided by these simulations successfully achieved low-temperature crystallization of phase-pure alpha-formamidinium lead iodide.