By combining temperature-dependent x-ray diffraction (XRD) with temperature-dependent Raman scattering, we have characterized the structural transitions and lattice dynamics of the hybrid organic–inorganic perovskite CH3NH3PbI3. The XRD measurements cover distinct phases between 15 K and 370 K and demonstrate a general positive thermal expansion. Clear anomalies are found around the transition temperatures. The temperature evolution of the lattice constants reveals that the transition at 160 K/330 K is of the first-/second-order type. Raman measurements uncover three strong low-frequency modes, which can be ascribed to the vibration of the Pb/I atoms. The temperature evolution of the modes clearly catches these transitions at 160 K and 330 K, and confirms the transition types, which are exactly consistent with the XRD results. The present study may set an experimental basis to understand the high conversion efficiency in methylammonium lead iodide.
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