Scalable Route to the Fabrication of CH3NH3PbI3 Perovskite Thin Films by Electrodeposition and Vapor Conversion

Hybrid halide perovskite thin films are applicable in a wide range of devices such as light-emitting diodes, solar cells, and photodetectors. The optoelectronic properties of perovskites together with their simple and inexpensive film deposition methods make these materials a viable alternative to established materials in these devices. However, the potential of perovskite materials is compromised by the limitations of the existing deposition methods, which suffer from trade-off among suitability for large-scale industrial production in a batch or roll-to-roll manner, deposition area, film quality, and costs. We addressed these limitations by developing a deposition method that is inexpensive, applicable to large substrate areas, scalable, and yields high-quality perovskite films. In this study, the low-cost electrodeposition (ED) method and sequential exposure to reagent vapors produce CH₃NH₃PbI₃ perovskite films with thickness nonuniformity below 9% on a centimeter scale. PbO₂ films are electrodeposited first and then undergo two vapor conversion steps, with HI vapor in the first step and CH₃NH₃I vapor in the second step. The second step yields CH₃NH₃PbI₃ films that are continuous and consist of micrometer-sized grains. This process allows the preparation of both α- and β-phase CH₃NH₃PbI₃ films, offers a simple means to control the film thickness, and works over a wide range of film thicknesses. In this work, films with thicknesses ranging from 100 nm to 10 μm were prepared. ED and vapor conversion are inherently scalable techniques and hence the process described herein could benefit application areas in which large device areas and throughput are required, such as the production of solar cells.