Determination of the structural phase and octahedral rotation angle in halide perovskites

dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

doi:10.1063/1.5017537

Title: Determination of the structural phase and octahedral rotation angle in halide perovskites

Journal Article · Mon Feb 12 00:00:00 EST 2018 · Applied Physics Letters

DOI:https://doi.org/10.1063/1.5017537· OSTI ID:1434015

^[1];

^[1]; Bizarri, Gregory ^[2]; Perrodin, Didier ^[2]; Shalapska, Tetiana ^[2]; Bourret, Edith ^[2]; Ciston, Jim ^[1]; Dahmen, Ulrich ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy, Molecular Foundry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr₃, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr₃ at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1434015

Alternate ID(s):: OSTI ID: 1420206

Journal Information:: Applied Physics Letters, Vol. 112, Issue 7; ISSN 0003-6951

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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Atomic‐Resolution Imaging of Halide Perovskites Using Electron Microscopy Song, Kepeng; Liu, Lingmei; Zhang, Daliang Advanced Energy Materials, Vol. 10, Issue 26 https://doi.org/10.1002/aenm.201904006	journal	February 2020
Pressure-induced strong ferroelectric polarization in tetra-phase perovskite CsPbBr ₃ Zhao, Yu-Qing; Ma, Qi-Rui; Liu, Biao Physical Chemistry Chemical Physics, Vol. 20, Issue 21 https://doi.org/10.1039/c8cp01338a	journal	January 2018