Adverse Effects of Excess Residual PbI2 on Photovoltaic Performance, Charge Separation, and Trap-State Properties in Mesoporous Structured Perovskite Solar Cells

Organic-inorganic halide perovskite solar cells have rapidly come to prominence in the photovoltaic field. In this context, CH3NH3PbI3, as the most widely adopted active layer, has been attracting great attention. Generally, in a CH3NH3PbI3 layer, unreacted PbI2 inevitably coexists with the perovskite crystals, especially following a two-step fabrication process. There appears to be a consensus that an appropriate amount of unreacted PbI2 is beneficial to the overall photovoltaic performance of a device, the only disadvantageous aspect of excess residual PbI2 being viewed as its insulating nature. However, the further development of such perovskite-based devices requires a deeper understanding of the role of residual PbI2. In this work, PbI2-enriched and PbI2-controlled perovskite films, as two extreme cases, have been prepared by modulating the crystallinity of a pre-deposited PbI2 film. The effects of excess residual PbI2 have been elucidated on the basis of spectroscopic and optoelectronic studies. The initial charge separation, the trap-state density, and the trap-state distribution have all been found to be adversely affected in PbI2-enriched devices, to the detriment of photovoltaic performance. This leads to a biphasic recombination process and accelerates the charge carrier recombination dynamics.