The chemical origins of charge recombination centers in lead-based organohalide perovskites were investigated using a combination of quantitative solution chemistry, X-ray diffraction, and time-resolved photoluminescence spectroscopy. We explored the complex, concentration-dependent solution equilibria among iodoplumbate coordination complexes that have been implicated as potential midgap states in organohalide perovskites. High concentrations of PbI2, PbI3-, and PbI42- were found in precursor solutions that match those used to deposit perovskite films for solar cell applications. We found that the concentration of tetraiodoplumbate PbI42- is uniquely correlated with the density of charge recombination centers found in the final perovskite films regardless of the lead precursor used to cast the films. However, mixed-halide perovskites commonly referred to as CH3NH3PbI3-xClx suppressed the formation of PbI42- in comparison to perovskites that included only iodide, which is consistent with the longer charge carrier lifetimes reported in mixed-halide perovskites. These findings bring a molecular-level view to the chemical origins of charge recombination centers that provides a fundamental basis from which to understand the reported improvement in uniformity of perovskite films and devices deposited using sequential methods. These findings also suggest new approaches to control the formation of defect precursors during the deposition of organohalide perovskite absorbers.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films