Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite

By Alexander N. Beecher, O. Semonin, J. Skelton, Jarvist Moore Frost, M. Terban, Haowei Zhai, A. Alataş, J. Owen, Aron Walsh, Simon J. L. Billinge Columbia University Chemistry Dept. and 5 more. 2016

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Lead halide perovskites such as methylammonium lead triiodide (CH3NH3PbI3) have outstanding optical and electronic properties for photovoltaic applications, yet a full understanding of how this solution-processable material works so well is currently missing. Previous research has revealed that CH3NH3PbI3 possesses multiple forms of static disorder regardless of preparation method, which is surprising in light of its excellent performance. Using high energy resolution inelastic X-ray (HERIX) scattering, we measure phonon dispersions in CH3NH3PbI3 and find direct evidence for another form of disorder in single crystals: large-amplitude anharmonic zone edge rotational instabilities of the PbI6 octahedra that persist to room temperature and above, left over from structural phase transitions that take place tens to hundreds of degrees below. Phonon calculations show that the orientations of the methylammonium (CH3NH3+) couple strongly and cooperatively to these modes. The result is a noncentrosymmetric, insta...

Subfields: Atomic and Molecular Physics, and Optics, Electrical and Electronic Engineering, Materials Chemistry

View Paper: https://www.semanticscholar.org/paper/4f252fe472d86a7021fb501a96514a0ff01704d7