Molecular orientational melting within a lead-halide octahedron framework: The order-disorder transition in CH_3NH_3PbBr_3

摘要

Lead-halide organic-inorganic perovskites consist of an inorganic host framework with an organic molecule occupying the interstitial space. The structure and dynamics of these materials have been heavily studied recently due to interest in their exceptional photovoltaic properties. We combine inelastic neutron scattering, Raman spectroscopy, and quasielastic neutron scattering to study the temperature dependent dynamics of the molecular cation in CH_3NH_3PbBr_3. By applying high resolution quasielastic neutron scattering, we confirm the [CH_3NH_3]~+ ions are static in the low temperature orthorhombic phase yet become dynamic above 150 K where a series of structural transitions occur. This molecularmelting is accompanied by a temporal broadening in the intramolecular modes probed through high energy inelastic spectroscopy. Simultaneous Ramanmeasurements, a strictly |Q| = 0 probe, are suggestive that this broadening is due to local variations in the crystal field environment around the hydrogen atoms. These results confirm the strong role of hydrogen bonding and also a coupling between molecular and framework dynamics.