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 2 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.
Bibliographical noteFunding Information:
The work of L.A.M., E.M.H., F.W., L.McG., J.V., H.J.B., and B.E. is part of the Dutch Research Council (NWO) and was performed at the research institute AMOLF. The work of L.A.M. and L.McG. was supported by NWO Vidi grant 016.Vidi.179.005. The work of Y.W.W., Y.K.J., and A.W. was supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018M3D1A1058536). Y.W.W., Y.K.J., and A.W. are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1).
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