Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites

Sebastián Caicedo-Dávila; Adi Cohen; Silvia G. Motti; Masahiko Isobe; Kyle M. McCall; Manuel Grumet; Maksym V. Kovalenko; Omer Yaffe; Laura M. Herz; Douglas H. Fabini; David A. Egger

doi:10.1038/s41467-024-48581-x

Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites

Sebastián Caicedo-Dávila, Adi Cohen, Silvia G. Motti, Masahiko Isobe, Kyle M. McCall, Manuel Grumet, Maksym V. Kovalenko, Omer Yaffe, Laura M. Herz, Douglas H. Fabini^*, David A. Egger^*

^*Corresponding author for this work

Department of Chemical and Biological Physics

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

Halide perovskites show great optoelectronic performance, but their favorable properties are paired with unusually strong anharmonicity. It was proposed that this combination derives from the ns² electron configuration of octahedral cations and associated pseudo-Jahn–Teller effect. We show that such cations are not a prerequisite for the strong anharmonicity and low-energy lattice dynamics encountered in these materials. We combine X-ray diffraction, infrared and Raman spectroscopies, and molecular dynamics to contrast the lattice dynamics of CsSrBr₃ with those of CsPbBr₃, two compounds that are structurally similar but with the former lacking ns² cations with the propensity to form electron lone pairs. We exploit low-frequency diffusive Raman scattering, nominally symmetry-forbidden in the cubic phase, as a fingerprint of anharmonicity and reveal that low-frequency tilting occurs irrespective of octahedral cation electron configuration. This highlights the role of structure in perovskite lattice dynamics, providing design rules for the emerging class of soft perovskite semiconductors.

Original language	English
Article number	4184
Journal	Nature Communications
Volume	15
DOIs	https://doi.org/10.1038/s41467-024-48581-x
Publication status	Published Online - 17 May 2024

Funding

Funding provided by the Alexander von Humboldt-Foundation in the framework of the Sofja Kovalevskaja Award, endowed by the German Federal Ministry of Education and Research, by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) via Germany’s Excellence Strategy - EXC 2089/1-390776260, and by TU Munich - IAS, funded by the German Excellence Initiative and the European Union Seventh Framework Programme under Grant Agreement No. 291763, are gratefully acknowledged. Funding was provided by the Engineering and Physical Sciences Research Council (EPSRC), UK. The Gauss Centre for Supercomputing eV is acknowledged for providing computing time through the John von Neumann Institute for Computing on the GCS Supercomputer JUWELS at Jülich Supercomputing Centre. D.H.F. gratefully acknowledges financial support from the Alexander von Humboldt Foundation and the Max Planck Society. D.H.F. thanks Maximilian A. Plass for assistance with flame-sealing the Raman capillaries. K.M.M. and M.V.K. acknowledge financial support by ETH Zürich through the ETH+ Project SynMatLab Laboratory for Multiscale Materials Synthesis. Publisher Copyright: © The Author(s) 2024.

All Science Journal Classification (ASJC) codes

General Chemistry
General Biochemistry,Genetics and Molecular Biology
General Physics and Astronomy

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Caicedo-Dávila, S., Cohen, A., Motti, S. G., Isobe, M., McCall, K. M., Grumet, M., Kovalenko, M. V., Yaffe, O., Herz, L. M., Fabini, D. H., & Egger, D. A. (2024). Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites. Nature Communications, 15, Article 4184. Advance online publication. https://doi.org/10.1038/s41467-024-48581-x

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abstract = "Halide perovskites show great optoelectronic performance, but their favorable properties are paired with unusually strong anharmonicity. It was proposed that this combination derives from the ns2 electron configuration of octahedral cations and associated pseudo-Jahn–Teller effect. We show that such cations are not a prerequisite for the strong anharmonicity and low-energy lattice dynamics encountered in these materials. We combine X-ray diffraction, infrared and Raman spectroscopies, and molecular dynamics to contrast the lattice dynamics of CsSrBr3 with those of CsPbBr3, two compounds that are structurally similar but with the former lacking ns2 cations with the propensity to form electron lone pairs. We exploit low-frequency diffusive Raman scattering, nominally symmetry-forbidden in the cubic phase, as a fingerprint of anharmonicity and reveal that low-frequency tilting occurs irrespective of octahedral cation electron configuration. This highlights the role of structure in perovskite lattice dynamics, providing design rules for the emerging class of soft perovskite semiconductors.",

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Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites

Abstract

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