Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites

Matan Menahem; Zhenbang Dai; Sigalit Aharon; Rituraj Sharma; Maor Asher; Yael Diskin-Posner; Roman Korobko; Andrew M Rappe; Omer Yaffe

doi:10.1021/acsnano.1c02022

Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites

Matan Menahem, Zhenbang Dai, Sigalit Aharon, Rituraj Sharma, Maor Asher, Yael Diskin-Posner, Roman Korobko, Andrew M Rappe, Omer Yaffe^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

Recent investigations of two-dimensional (2D) hybrid organic-inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron-phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA)2PbI4 and (PhE)2PbI4] to their three-dimensional (3D) counterpart, MAPbI3. Comparison to the simpler, 3D MAPbI3 crystal shows clear similarities with the structural dynamics of (BA)2PbI4 and (PhE)2PbI4 across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order-disorder phase transition of (BA)2PbI4 (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.

Original language	English
Pages (from-to)	10153-10162
Number of pages	10
Journal	ACS Nano
Volume	15
Issue number	6
Early online date	18 May 2021
DOIs	https://doi.org/10.1021/acsnano.1c02022
Publication status	Published - 22 Jun 2021

Funding

The authors would like to thank Dr. Tsachi Livneh (NRC) for fruitful discussions and Dr. Lior Segev (WIS) for developing the Raman software. O.Y. acknowledges funding from ISF(1861/17), BSF (grant no. 2016650), ERC (850041 - ANHARMONIC). Z.D. acknowledges support from the US National Science Foundation, under grant DMR-1719353. A.M.R. acknowledges support from the Office of Naval Research under grant N00014-20-1-2701. The authors acknowledge computational support from the High-Performance Computing Modernization Office of the US Department of Defense.

All Science Journal Classification (ASJC) codes

General Materials Science
General Engineering
General Physics and Astronomy

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title = "Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites",

abstract = "Recent investigations of two-dimensional (2D) hybrid organic-inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron-phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA)2PbI4 and (PhE)2PbI4] to their three-dimensional (3D) counterpart, MAPbI3. Comparison to the simpler, 3D MAPbI3 crystal shows clear similarities with the structural dynamics of (BA)2PbI4 and (PhE)2PbI4 across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order-disorder phase transition of (BA)2PbI4 (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.",

author = "Matan Menahem and Zhenbang Dai and Sigalit Aharon and Rituraj Sharma and Maor Asher and Yael Diskin-Posner and Roman Korobko and Rappe, {Andrew M} and Omer Yaffe",

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AU - Sharma, Rituraj

AU - Asher, Maor

AU - Diskin-Posner, Yael

AU - Korobko, Roman

AU - Rappe, Andrew M

AU - Yaffe, Omer

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Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites

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