Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport. However, it is yet to be understood how the counter-intuitive vertical orientations of 2D perovskite layers on substrates can be obtained. Here we report a formation mechanism of such vertically orientated 2D perovskite in which the nucleation and growth arise from the liquid–air interface. As a consequence, choice of substrates can be liberal from polymers to metal oxides depending on targeted application. We also demonstrate control over the degree of preferential orientation of the 2D perovskite layers and its drastic impact on device performance.

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.

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