Lattice Compression Increases the Activation Barrier for Phase Segregation in Mixed-Halide Perovskites
The bandgap tunability of mixed-halide perovskites makes them promising candidates for light emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single-halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. 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 two orders of magnitude on increasing the pressure to 0.3 GPa. We explain this reduction from a compression-induced increase of the activation energy for halide 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.
|Journal||ACS Energy Lett.|
Muscarella, L.A, Hutter, E.M, Wittmann, F, Woo, Y.W, Jung, Y.-K, McGovern, L, … Ehrler, B. (2020). Lattice Compression Increases the Activation Barrier for Phase Segregation in Mixed-Halide Perovskites. ACS Energy Lett., 5, 3152–3158. doi:10.1021/acsenergylett.0c01474