Understanding the Formation of Vertical Orientation in Two-dimensional Metal Halide Perovskite Thin Films

Metal halide perovskites have demonstrated strong potential for optoelectronic applications. Particularly, two-dimensional (2D) perovskites have emerged to be promising materials due to their tunable properties and superior stability compared to their three-dimensional counterparts. For high device performance, 2D perovskites need a vertical crystallographic orientation with respect to the electrodes to achieve efficient charge transport. However, the vertical orientation is difficult to achieve with various compositions due to a lack of understanding of the thin film nucleation and growth processes. Here we report a general crystallization mechanism for 2D perovskites, where solvent evaporation and crystal growth compete to influence the level of supersaturation and a low supersaturation is necessary to crystallize vertically oriented thin films starting from nucleation at the liquid-air interface. Factors influencing the supersaturation and crystallization dynamics, such as choices of organic spacers, solvents, and solvent drying rate, have a strong influence on the degree of crystallographic orientation. With this understanding of crystallization mechanism, we demonstrate direct crystallization of thin films with strong vertical orientation using three different organic spacers without any additives, and the vertically oriented 2D perovskites result in efficient and stable solar cell operation.