Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6

Abstract CuInP2S6 (CIPS) is an emerging 2D ferroelectric material known for disrupting spatial inversion symmetry due to Cu(I) position switching. Its ferroelectricity strongly relies on the Cu(I) atom/ion occupation ordering and dynamics. Nevertheless, the accurate Cu(I) occupations and correlated...

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Main Authors: Changjin Guo, Jiajun Zhu, Xiali Liang, Caifu Wen, Jiyang Xie, Chengding Gu, Wanbiao Hu
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54229-7
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author Changjin Guo
Jiajun Zhu
Xiali Liang
Caifu Wen
Jiyang Xie
Chengding Gu
Wanbiao Hu
author_facet Changjin Guo
Jiajun Zhu
Xiali Liang
Caifu Wen
Jiyang Xie
Chengding Gu
Wanbiao Hu
author_sort Changjin Guo
collection DOAJ
description Abstract CuInP2S6 (CIPS) is an emerging 2D ferroelectric material known for disrupting spatial inversion symmetry due to Cu(I) position switching. Its ferroelectricity strongly relies on the Cu(I) atom/ion occupation ordering and dynamics. Nevertheless, the accurate Cu(I) occupations and correlated migration dynamics under the externally applied energy, which are key to unlocking ferroelectric properties, remain controversial and unresolved. Herein, an atomic-level direct imaging through aberration-corrected scanning transmission electron microscopy is performed to precisely trace the Cu(I) dynamic behaviours under electron-beam irradiation along (100)-CIPS. It clearly demonstrates that Cu(I) possesses multiple occupations, and Cu(I) could migrate to the lattice, vacancy, interstitial and interlayer sites between the InS6 octahedral skeletons of CIPS to form local Cu x InP2S6 (x = 2-4) structure. Cu(I) multi-occupations induced lattice stress results in a layer sliding along the b-axis direction generating a sliding size of 1/6 b lattice constant. The Cu x InP2S6 (x = 2-4) exists in a type of dynamic structure, only metastable with electron dose over 50 e− Å−2, thus generating a dynamic process of $${\mbox{C}}{{\mbox{u}}}_{x}{\mbox{In}}{{\mbox{P}}}_{2}{{\mbox{S}}}_{6}(x=2-4)\rightleftharpoons {\mbox{CuIn}}{{\mbox{P}}}_{2}{{\mbox{S}}}_{6}$$ C u x In P 2 S 6 ( x = 2 − 4 ) ⇌ CuIn P 2 S 6 , a completely unreported phenomenon. These findings shed light on the unveiled mechanism underlying Cu(I) migration in CIPS, providing crucial insights into the fundamental processes that govern its ferroelectric properties.
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spelling doaj-art-d7d1cf92cec5458a97685df57ea7c4ea2025-08-20T02:22:24ZengNature PortfolioNature Communications2041-17232024-11-011511810.1038/s41467-024-54229-7Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6Changjin Guo0Jiajun Zhu1Xiali Liang2Caifu Wen3Jiyang Xie4Chengding Gu5Wanbiao Hu6Yunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityYunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan UniversityAbstract CuInP2S6 (CIPS) is an emerging 2D ferroelectric material known for disrupting spatial inversion symmetry due to Cu(I) position switching. Its ferroelectricity strongly relies on the Cu(I) atom/ion occupation ordering and dynamics. Nevertheless, the accurate Cu(I) occupations and correlated migration dynamics under the externally applied energy, which are key to unlocking ferroelectric properties, remain controversial and unresolved. Herein, an atomic-level direct imaging through aberration-corrected scanning transmission electron microscopy is performed to precisely trace the Cu(I) dynamic behaviours under electron-beam irradiation along (100)-CIPS. It clearly demonstrates that Cu(I) possesses multiple occupations, and Cu(I) could migrate to the lattice, vacancy, interstitial and interlayer sites between the InS6 octahedral skeletons of CIPS to form local Cu x InP2S6 (x = 2-4) structure. Cu(I) multi-occupations induced lattice stress results in a layer sliding along the b-axis direction generating a sliding size of 1/6 b lattice constant. The Cu x InP2S6 (x = 2-4) exists in a type of dynamic structure, only metastable with electron dose over 50 e− Å−2, thus generating a dynamic process of $${\mbox{C}}{{\mbox{u}}}_{x}{\mbox{In}}{{\mbox{P}}}_{2}{{\mbox{S}}}_{6}(x=2-4)\rightleftharpoons {\mbox{CuIn}}{{\mbox{P}}}_{2}{{\mbox{S}}}_{6}$$ C u x In P 2 S 6 ( x = 2 − 4 ) ⇌ CuIn P 2 S 6 , a completely unreported phenomenon. These findings shed light on the unveiled mechanism underlying Cu(I) migration in CIPS, providing crucial insights into the fundamental processes that govern its ferroelectric properties.https://doi.org/10.1038/s41467-024-54229-7
spellingShingle Changjin Guo
Jiajun Zhu
Xiali Liang
Caifu Wen
Jiyang Xie
Chengding Gu
Wanbiao Hu
Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
Nature Communications
title Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
title_full Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
title_fullStr Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
title_full_unstemmed Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
title_short Atomic-level direct imaging for Cu(I) multiple occupations and migration in 2D ferroelectric CuInP2S6
title_sort atomic level direct imaging for cu i multiple occupations and migration in 2d ferroelectric cuinp2s6
url https://doi.org/10.1038/s41467-024-54229-7
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