Dubajic, M.; Neilson, J.R.; Klarbring, J.; Liang, X.; Bird, S.A.; Rule, K.C.; Auckett, J.E.; Selby, T.A.; Tumen-Ulzii, G.; Lu, Y.; Jung, Y.K.; Chosy, C.; Wei, Z.; Boeije, Y.; Zimmermann, M.v.; Pusch, A.; Gu, L.; Jia, X.; Wu, Q.; Trowbridge, J.C.; Mozur, E.M.; Minelli, A.; Roth, N.; Orr, K.W.P.; Mahboubi Soufiani, A.; Kahmann, S.; Kabakova, I.; Ding, J.; Wu, T.; Conibeer, G.J.; Bremner, S.P.; Nielsen, M.P.; Walsh, A.; Stranks, S.D.: Dynamic nanodomains dictate macroscopic properties in lead halide perovskites. Nature Nanotechnology 20 (2025), p. 755-763
10.1038/s41565-025-01917-0
Open Accesn Version
Abstract:
Lead halide perovskites have emerged as promising materials for solar energy conversion and X-ray detection owing to their remarkable optoelectronic properties. However, the microscopic origins of their superior performance remain unclear. Here we show that low-symmetry dynamic nanodomains present in the high-symmetry average cubic phases, whose characteristics are dictated by the A-site cation, govern the macroscopic behaviour. We combine X-ray diffuse scattering, inelastic neutron spectroscopy, hyperspectral photoluminescence microscopy and machine-learning-assisted molecular dynamics simulations to directly correlate local nanoscale dynamics with macroscopic optoelectronic response. Our approach reveals that methylammonium-based perovskites form densely packed, anisotropic dynamic nanodomains with out-of-phase octahedral tilting, whereas formamidinium-based systems develop sparse, isotropic, spherical nanodomains with in-phase tilting, even when crystallography reveals cubic symmetry on average. We demonstrate that these sparsely distributed isotropic nanodomains present in formamidinium-based systems reduce electronic dynamic disorder, resulting in a beneficial optoelectronic response, thereby enhancing the performance of formamidinium-based lead halide perovskite devices. By elucidating the influence of the A-site cation on local dynamic nanodomains, and consequently, on the macroscopic properties, we propose leveraging this relationship to engineer the optoelectronic response of these materials, propelling further advancements in perovskite-based photovoltaics, optoelectronics and X-ray imaging.