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.
| Original language | English |
|---|---|
| Pages (from-to) | 755-763 |
| Number of pages | 9 |
| Journal | Nature Nanotechnology |
| Volume | 20 |
| Issue number | 6 |
| DOIs | |
| State | Published - Jun 2025 |
Funding
M.D. acknowledges helpful discussions with E. Salje, R. A. Mole, W. J. Baldwin, T. Doherty, M. Spasovski and Lj. Stojković. We thank the Diamond Light Source for providing beamtime at the I19-1 (proposal no. CY33123). We would like to acknowledge the Australian Nuclear Science and Technology Organisation beamtime received on Sika and Taipan through proposal nos. P14150 and DB9600. We also thank the staff from the Mark Wainwright Analytical Centre at UNSW Sydney for the X-ray and differential scanning calorimetry measurements. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/X035859/1), this work also used the ARCHER2 UK National Supercomputing Service ( https://www.archer2.ac.uk ). The training of the machine learning force fields were enabled by the Berzelius resource provided by the Knut and Alice Wallenberg Foundation at the National Supercomputer Centre. We acknowledge the National Academic Infrastructure for Supercomputing in Sweden (NAISS) partially funded by the Swedish Research Council through grant agreement no. 2022-06725 for awarding this project access to the LUMI supercomputer, owned by the EuroHPC Joint Undertaking, hosted by CSC (Finland) and the LUMI consortium. This work was supported by the National Natural Science Foundation of China (grant nos. 51572037, 91648109, 51335002 and 51702024), the Natural Science Foundation of Jiangsu Province (grant no. BK20200981) and Changzhou Sci Tech Program (grant no. CJ20190050). This work was supported by the Australian Research Council Discovery Project (ARC DP) (DP190101973). M.D. acknowledges support by the UKRI guarantee funding for Marie Skłodowska-Curie Actions Postdoctoral Fellowships 2022 (EP/Y024648/1), by AINSE Limited through a PGRA award and by Churchill College at the University of Cambridge. M.P.N. recognizes support from the UNSW Scientia Program and an ARC DECRA Fellowship (grant no. DE230100382). J.R.N., A.M. and N.R. acknowledge A. L. Goodwin and an ERC Grant (advanced grant no. 788144) for support. J.R.N. acknowledges the Leverhulme Trust for granting a Visiting Professorship at the Inorganic Chemistry Laboratory, University of Oxford. The work at Colorado State University was supported by grant no. DE-SC0023316 funded by the US Department of Energy, Office of Science. G.T.-U. acknowledges funding from a Marie Skłodowska-Curie Postdoctoral Fellowship via UKRI Horizon Europe Guarantee, grant no. EP/Y016912/1. Y.-K.J. acknowledges UKRI guarantee funding for Marie Skłodowska-Curie Postdoctoral Fellowship 2021 (EP/X025756/1). T.A.S. acknowledges funding from EPSRC Cambridge NanoDTC (EP/S022953/1). C.C. acknowledges support from a Marshall Scholarship, Winton Scholarship and the Cambridge Trust. Y.B. acknowledges support from a Winton Scholarship. T.W. acknowledges support from the Global STEM Professorship, the Hong Kong Innovation and Technology Commission (MHP/233/23) and the Research Grants Council under the General Research Fund (P0051623). S.K. is grateful for an Early Career Fellowship supported by the Leverhulme Trust (ECF-2022-593) and the Isaac Newton Trust (22.08(i)). K.W.P.O. acknowledges an EPSRC studentship (project reference no. 2275833). J.K. acknowledges support from the Swedish Research Council (VR) program no. 2021-00486. We thank the Leverhulme Trust (RPG-2021-191) for funding. We acknowledge Deutsches Elektronen-Synchrotron (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank F. Igoa and K. Köhler for assistance in using the P21.1 beamline. Some of the equipment we utilized on P21.1 was funded by the German Federal Ministry of Education and Research (BMBF) under grant no. 05K22RF1. S.D.S. acknowledges the Royal Society and Tata Group (UF150033 and URF\R\221026).