An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Wenjuan Wei; Wei Li; Keith T. Butler; Guoqiang Feng; Christopher J. Howard; Michael A. Carpenter; Peixiang Lu; Aron Walsh; Anthony K. Cheetham

doi:10.1002/anie.201803176

An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Wenjuan Wei, Wei Li, Keith T. Butler, Guoqiang Feng, Christopher J. Howard, Michael A. Carpenter, Peixiang Lu, Aron Walsh, Anthony K. Cheetham

Department of Materials Science and Engineering

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

40 Citations (Scopus)

Abstract

The driving forces for the phase transitions of ABX₃ hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH₃NH₃][Mn(N₃)₃], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first-order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K⁻¹ mol⁻¹) is observed between the low- and high-temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

Original language	English
Pages (from-to)	8932-8936
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	29
DOIs	https://doi.org/10.1002/anie.201803176
Publication status	Published - 2018 Jul 16

Bibliographical note

Funding Information:
The authors acknowledge the funding support from the National Natural Science Foundation of China (Grant no. 21571072). W.W., G.F., W.L. and P.L. thank the Fundamental Research Funds for the Central Universities, HUST (Grant no. 2017KFXKJC002). W.L. is grateful to Prof. Song Gao for his illuminating suggestions.

Funding Information:
The authors acknowledge the funding support from the National Natural Science Foundation of China (Grant no.

Funding Information:
21571072). W.W., G.F., W.L. and P.L. thank the Fundamental Research Funds for the Central Universities, HUST (Grant no. 2017KFXKJC002). W.L. is grateful to Prof. Song Gao for his illuminating suggestions.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.201803176

Cite this

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title = "An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite",

abstract = "The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first-order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low- and high-temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.",

author = "Wenjuan Wei and Wei Li and Butler, {Keith T.} and Guoqiang Feng and Howard, {Christopher J.} and Carpenter, {Michael A.} and Peixiang Lu and Aron Walsh and Cheetham, {Anthony K.}",

note = "Funding Information: The authors acknowledge the funding support from the National Natural Science Foundation of China (Grant no. 21571072). W.W., G.F., W.L. and P.L. thank the Fundamental Research Funds for the Central Universities, HUST (Grant no. 2017KFXKJC002). W.L. is grateful to Prof. Song Gao for his illuminating suggestions. Funding Information: The authors acknowledge the funding support from the National Natural Science Foundation of China (Grant no. Funding Information: 21571072). W.W., G.F., W.L. and P.L. thank the Fundamental Research Funds for the Central Universities, HUST (Grant no. 2017KFXKJC002). W.L. is grateful to Prof. Song Gao for his illuminating suggestions. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Carpenter, Michael A.

AU - Lu, Peixiang

AU - Walsh, Aron

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N2 - The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first-order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low- and high-temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

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An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Abstract

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