Abstract
Metal halide perovskites, with an ABX3 crystal structure, possess excellent photophysical properties for (opto)electronic applications including photovoltaics, light-emitting diodes, photodetectors and transistors. To pave the pathway towards commercial applications, enormous efforts have been made to obtain high-performance perovskite-based devices. The octahedral unit is considered to be the fundamental and functional unit of halide perovskite materials, consisting of a central B cation surrounded by six X anions, with typical dimensions of 5−6 Å. One promising pathway towards stable and high-performance perovskite devices is to manipulate this octahedral unit. Although rational engineering of octahedra has been used in oxide perovskites to unlock various functionalities, analogous targeted work has been relatively underexplored in halide perovskites. Here, we present fundamental concepts regarding octahedral configurations in metal halide perovskites and its effects on crystal structures, photophysical properties and device performance. We outline techniques that can be used for characterizing octahedral units and summarize different approaches to rationally manipulate these units. Finally, we discuss the challenges and outlook for future research to align octahedral units with device investigations.
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Acknowledgements
Yong Wang thanks the National Science Fund for Excellent Young Scholars (Overseas), Top Talent Project of West Lake Pearl Project, National Natural Science Foundation of China (numbers 52302315 and 62474157), and the talent project of ZJU-Hangzhou Global Scientific and Technological Innovation Center (number 02170000-K02013017). D.Y. thanks the project of National Natural Science Foundation of China (number 61721005). Yu Wang thanks the European Union’s Horizon 2020 research and innovation programme with a Marie Skłodowska-Curie grant agreement number 956270. F.G. thanks the project of Wallenberg Foundation (number 2019.0082). S.D.S. thanks the Royal Society and Tata Group (UF150033). T.A.S.D. acknowledges the support of an Ernest Oppenheimer Research fellowship and a Schmidt Science fellowship.
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Yong Wang conceived the idea. D.Y., F.G. and S.D.S. supported this work. Yong Wang, Yu Wang and T.A.S.D. wrote the original draft. All the authors reviewed and edited the draft.
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Wang, Y., Wang, Y., Doherty, T.A.S. et al. Octahedral units in halide perovskites. Nat Rev Chem (2025). https://doi.org/10.1038/s41570-025-00687-6
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DOI: https://doi.org/10.1038/s41570-025-00687-6
