Valine-Modified PbI2 for the Growth of Pinhole-Free Lead Halide Perovskite Thin Films by Vapor–Solid Reaction

Abstract

In recent years, the efficiency of perovskite solar cells (PSCs) has rapidly increased, making PSCs commercially viable and able to compete with silicon solar cells. However, the technology for large-scale production of perovskite thin films still poses a significant challenge to the commercialization of PSCs. This is mainly because the thickness of the perovskite light-absorbing film is less than 1 μm and easily produces pinholes during large-scale production, causing serious charge recombination and reducing the efficiency of the device. As a result, the efficiencies of most large-scale PSC modules are significantly lower than those of small-size devices. Vapor-reaction technology is considered a crucial method to enhance the uniformity of perovskite thin films. However, current techniques are not yet advanced enough to deposit pinhole-free perovskite thin films on a large scale. One major challenge is that lead iodide (PbI2) precursor thin films have a tendency to develop a sheet-like structure with a loose morphology, which contributes to the formation of pinholes in the perovskite film. Additionally, uncoordinated Pb2+ could be easily generated in the PbI2 film during thermal evaporation, causing an increase in trap-states in the perovskite crystal. To address this, we developed a valine treatment process in this study to change the preferred orientation of PbI2 from a sheet-like to a particle-like aggregate and obtained compact PbI2 thin films. Meanwhile, this valine vapor treatment can significantly reduce the uncoordinated Pb2+ in PbI2 films. Based on this, we successfully prepared pinhole-free perovskite thin films using a vapor–solid reaction. Perovskite films based on these valine-treated PbI2 exhibited a reduced trap density and significantly improved PSCs’ performance, with a maximum efficiency exceeding 21%. Large-area PSC mini-modules (5 cm × 5 cm) produced from the perovskite film (30 cm × 30 cm) showed uniformly distributed power conversion efficiency values exceeding 17%, with the highest value reaching 18.78%. We believe that this facile valine vapor treatment holds great potential for the large-scale production of stable and high-efficiency PSC modules.