Proceedings of 13th Conference on Hybrid and Organic Photovoltaics (HOPV21)
Publication date: 11th May 2021
Halide perovskite semiconductors have recently gathered significant attention due to their intriguing optoelectronic properties combined with low-cost and simple fabrication method. In addition, the easy bandgap tunability of this material by changing the ratio of halides in the chemical composition, makes them promising candidate for LEDs and tandem solar cells in combination with silicon. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single halide. Phase segregation affects the homogeneity of the bandgap compromising the purity and the quality of the absorption/emission and therefore its applications. This segregation occurs through ion migration, which is also observed in pure-halide compositions, and whose control is essential to enhance lifetime and stability.
In this work, we investigate how pressure-induced compression of the unit cell volume affects the kinetics aspects of phase segregation in mixed halide perovskite MAPb(BrxI1-x)3 (where x is the bromide concentration equal to 25%, 50% and 70%). Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(BrxI1-x)3 reduce by ~2 orders of magnitude upon increasing pressure to 0.3 GPa. We interpret this change as a compression-induced difference in the activation energy for ion migration, which is supported by first-principle calculations. A similar mechanism occurs when the unit cell volume is reduced by incorporating a smaller cation. These findings reveal that stability with respect to halide segregation can be achieved either physically through compressive stress or chemically through compositional engineering and that in principle any iodide-bromide ratio can be thermodynamically stabilized by tuning the unit cell volume.
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