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

• DOI: 10.1038/s41467-024-48581-x
• Publication Date: 2024-05-17T05:01:55Z
• Authors: Sebastián Caicedo...; 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
• Keywords: Materials chemistry; Materials for energy and catalysis; Condensed Matter - Materials Science; Science; Q; Materials Science (cond-mat.mtrl-sci); FOS: Physical sciences; 540; 530; 01 natural sciences; solid state physics; Article; molecular dynamics; ddc:; 0104 chemical sciences; halide perovskites; Molecular and chemical physics; Materials chemistry; Materials for energy and catalysis

AbstractHalide 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.