3D halide perovskites used in light emitters and PV systems exhibit an unusualanharmonicity, which is not accounted for in nowadays descriptions of phonons andelectron-phonon coupling. Therefore, the low frequency lattice vibrations andrelaxations were investigated in single crystals of the four 3D hybrid organoleadperovskites, MAPbBr3, FAPbBr3, MAPbI3, and FAPbI3, at the Brillouin zone centerusing Raman and Brillouin scattering and at the zone boundary using inelasticneutron scattering. The temperature dependence of the PbX6 lattice modes in thefour compounds can be renormalized into universal curves and no soft vibration isobserved excluding a displacive-like transitional dynamics related to structural phasetransitions. The reorientational (pseudospin) motions of the molecular cations exhibita seemingly order-disorder character recalling that of plastic crystals, but attributedto a secondary order-parameter. At ultra-low frequency, a quasi-elastic componentevidenced by Brillouin scattering and associated to the unresolved central peakobserved in neutron scattering, is attributed to center of mass anharmonic motionsand rattling of the molecular cations in the perovskite cavities. 3D halide perovskitesare therefore in a very unusual situation where anharmonicity prevails. It is leading topartial, extensive and ultraslow critical and stochatic dynamics connected or not tostructural instabilities. The extensive disorder of the lattice at normal operationtemperatures for devices is similar to premelting where only long-range acousticnormal modes survive.[1] A.Létoublon, S. Paofai, B. Ruffle, P. Bourges, B. Hehlen, T. Michel, C.Ecolivet, O.Durand, S. Cordier, C. Katan, J. Even. Elastic Constants, Optical Phonons andMolecular Relaxations in the High Temperature Plastic Phase of the CH3NH3PbBr3Hybrid Perovskite. J. Phys. Chem.Lett. 7, 3776 (2016)[2]C. Katan, A. D. Mohite, J. Even, Entropy in halide perovskites, Nature Materials,17, 377-379 (2018)[3]A. Ferreira, A. Létoublon, S. Paofai, S. Raymond, C. Ecolivet, B. Ruffle, S.Cordier, C. Katan, M. I. Saidaminov, A. A. Zhumekenov, O. M. Bakr, J. Even, P.Bourges, Elastic softness of hybrid lead halide perovskites, Phys. Rev. Lett., 121,085502 (2018)[4] A. Ferreira, S. Paofai, A. Létoublon, J. Ollivier, S. Raymond, B. Hehlen, B. Rufflé,S. Cordier, C. Katan, J. Even & P. Bourges, Direct evidence of weakly dispersed andstrongly anharmonic optical phonons in hybrid perovskites, Comm. Phys. 3, 48(2020).[5] B. Hehlen, P. Bourges, B. Rufflé, S. Clément, R. Vialla, A. C. Ferreira, C.Ecolivet, S. Paofai, S. Cordier, C. Katan, A. Létoublon, J. Even, Pseudospin-phononpretransitional dynamics in lead halide hybrid perovskites, Phys. Rev. B, 105,024306 (2022)

3D halide perovskites used in light emitters and PV systems exhibit an unusual anharmonicity, which is not accounted for in nowadays descriptions of phonons and electron-phonon coupling. Therefore, the low frequency lattice vibrations and relaxations were investigated in single crystals of the four 3D hybrid organolead perovskites, MAPbBr3, FAPbBr3, MAPbI3, and FAPbI3, at the Brillouin zone center using Raman and Brillouin scattering and at the zone boundary using inelastic neutron scattering. The temperature dependence of the PbX6 lattice modes in the four compounds can berenormalized into universal curves and no soft vibration is observed excluding a displacive-like transitional dynamics related to structural phase transitions. The reorientational (pseudospin) motions of the molecular cations exhibit a seemingly order-disorder character recalling that of plastic crystals, but attributed to a secondary order-parameter. At ultra-low frequency, a quasi-elastic component evidenced by Brillouin scattering and associated to the unresolved central peak observed in neutron scattering, is attributed to center of mass anharmonic motions and rattling of the molecular cations in the perovskite cavities. 3D halide perovskites are therefore in a very unusualsituation where anharmonicity prevails. It is leading to partial, extensive and ultraslow critical and stochatic dynamics connected to structural instabilities. The extensive disorder of the lattice at normal operation temperatures for devices is similar to premelting where only long-range acoustic normal modes survive.

Lattice dynamics in 3D lead halide hybrid perovskites is analyzed together with the possible consequences for device applications

We determine the structural origin of an “atomic-spring-like effect”in a glassy silica-helium composite, which exhibits this mechanical property thatreversibly accumulates and restores energy at the subnanoscale based on a high-pressure experimental pair distribution function study combined with atom-scalemolecular simulations. These unexpected experimental results were obtained byusing a 3 μm spot size 61 keV X-ray beam and large area detector and bysubtracting the scattered intensity due to helium outside the sample from the silicasignal at the same focal point for each pressure point. The compression behavior ofthe glassy silica-helium composite is characterized on a structural level by the change from a uni- to bimodal distribution in the inter- tetrahedral distances in the amorphous isotropic structure of silica. We propose a simple characterization of this atomic-spring-like glass property using impedance spectroscopy measurements.

The low frequency lattice vibrations and relaxations are investigated in single crystals of the four 3D hybrid organolead perovskites, MAPbBr3, FAPbBr3, MAPbI3, and α-FAPbI3, at the Brillouin zone center using Raman and Brillouin scattering and at the zone boundary using inelastic neutron scattering. The temperature dependence of the PbX6 lattice modes in the four compounds can be renormalized into universal curves, highlighting a common vibrational dynamics at the cubic to tetragonal transition. In particular, no soft vibration is observed excluding a displacive-like transitional dynamics. The reorientational (pseudospin) motions of the molecular cations exhibit a seemingly order-disorder character recalling that of plastic crystals, but attributed to a secondary order-parameter. At ultra-low frequency, a quasi-elastic component evidenced by Brillouin scattering and associated to the unresolved central peak observed in neutron scattering, is attributed to center of mass anharmonic motions and rattling of the molecular cations in the perovskite cavities. Its partially unexpressed critical behavior at the transition points toward the general importance of defects in HOPs preventing the net divergence of order parameter correlations at the critical temperatures.

The low frequency lattice vibrations and relaxations are investigated in single crystals of the four 3Dhybrid organolead perovskites, MAPbBr3, FAPbBr3, MAPbI3, and FAPbI3, at the Brillouin zone centerusing Raman and Brillouin scattering and at the zone boundary using inelastic neutron scattering. Thetemperature dependence of the PbX6 lattice modes in the four compounds can be renormalized intouniversal curves and no soft vibration is observed excluding a displacive-like transitional dynamics. Thereorientational (pseudospin) motions of the molecular cations exhibit a seemingly order-disordercharacter recalling that of plastic crystals, but attributed to a secondary order-parameter. At ultra-lowfrequency, a quasi-elastic component evidenced by Brillouin scattering and associated to the unresolvedcentral peak observed in neutron scattering, is attributed to center of mass anharmonic motions andrattling of the molecular cations in the perovskite cavities.