Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br)

Weizhao Cai; Jiangang He; Hao Li; Rong Zhang; Dongzhou Zhang; Duck Young Chung; Tushar Bhowmick; Christopher Wolverton; Mercouri G. Kanatzidis; Shanti Deemyad

doi:10.1038/s41467-021-21836-7

Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg₃Te₂X₂ (X = Cl, Br)

Weizhao Cai, Jiangang He^*, Hao Li, Rong Zhang, Dongzhou Zhang, Duck Young Chung, Tushar Bhowmick, Christopher Wolverton, Mercouri G. Kanatzidis^*, Shanti Deemyad^*

^*Corresponding author for this work

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

8 Scopus citations

Abstract

Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase I2₁3 to R3 induced by pressure in two isostructural defect antiperovskites Hg₃Te₂Cl₂ (15.5 GPa) and Hg₃Te₂Br₂ (17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ₄, similar to the archetypal ferroelectric material BaTiO₃ at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg₃Te₂Br₂ with an unexpectedly stable R3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems.

Original language	English (US)
Article number	1509
Journal	Nature communications
Volume	12
Issue number	1
DOIs	https://doi.org/10.1038/s41467-021-21836-7
State	Published - Dec 1 2021

ASJC Scopus subject areas

Physics and Astronomy(all)
Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)

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10.1038/s41467-021-21836-7

Cite this

@article{fa2bba4ee303463c96c3a58bc2de7f9b,

title = "Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br)",

abstract = "Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase I213 to R3 induced by pressure in two isostructural defect antiperovskites Hg3Te2Cl2 (15.5 GPa) and Hg3Te2Br2 (17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ4, similar to the archetypal ferroelectric material BaTiO3 at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg3Te2Br2 with an unexpectedly stable R3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems.",

author = "Weizhao Cai and Jiangang He and Hao Li and Rong Zhang and Dongzhou Zhang and Chung, {Duck Young} and Tushar Bhowmick and Christopher Wolverton and Kanatzidis, {Mercouri G.} and Shanti Deemyad",

note = "Funding Information: The authors would like to acknowledge Dr. Haozhe Liu (HPSTAR) for allowing us to use the gearbox for helium loading and Dr. Przemys{\l}aw Dera (University of Hawaii at Manoa) for his kind demonstration of the ATREX software. We thank Dr. Jin-Ke Bao for valuable discussions, Dr. Sergy Tkachev for the assistance of helium gas loading, and Dr. Jesse Smith for experimental support of X-ray measurements. The high-pressure single crystal and powder X-ray diffraction data were respectively collected at 13-BM-C of GeoSoilEnviroCARS (The University of Chicago, Sector 13) and 16-ID-B of HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoi-lEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415), and Department of Energy-GeoSciences (DE-FG02-94ER14466). HPCAT operations are supported by DOE-NNSA{\textquoteright}s Office of Experimental Sciences. Use of the COMPRES-GSECARS gas loading system and PX2 was supported by COMPRES under NSF Cooperative Agreement EAR-1661511, and by GSECARS through NSF grant EAR-1634415 and DOE grant DE-FG02-94ER14466. Work at Argonne (sample preparation, characterization, and crystal growth) is supported by the U.S. DOE, Office of Basic Energy Science, Materials Science and Engineering Division. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This work at University of Utah was supported by the U.S. Department of Energy, Office of Science, Fusion Energy Sciences under Award Number DE-SC0020340 (S.D.). DFT calculations at Northwestern University acknowledge National Science Foundation through the MRSEC program (NSF-DMR 1720139) at the Materials Research Center. The authors acknowledge the computing resources provided by the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. Publisher Copyright: {\textcopyright} 2021, The Author(s).",

year = "2021",

month = dec,

day = "1",

doi = "10.1038/s41467-021-21836-7",

language = "English (US)",

volume = "12",

journal = "Nature Communications",

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T1 - Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br)

AU - Cai, Weizhao

AU - He, Jiangang

AU - Li, Hao

AU - Zhang, Rong

AU - Zhang, Dongzhou

AU - Chung, Duck Young

AU - Bhowmick, Tushar

AU - Wolverton, Christopher

AU - Kanatzidis, Mercouri G.

AU - Deemyad, Shanti

N1 - Funding Information: The authors would like to acknowledge Dr. Haozhe Liu (HPSTAR) for allowing us to use the gearbox for helium loading and Dr. Przemysław Dera (University of Hawaii at Manoa) for his kind demonstration of the ATREX software. We thank Dr. Jin-Ke Bao for valuable discussions, Dr. Sergy Tkachev for the assistance of helium gas loading, and Dr. Jesse Smith for experimental support of X-ray measurements. The high-pressure single crystal and powder X-ray diffraction data were respectively collected at 13-BM-C of GeoSoilEnviroCARS (The University of Chicago, Sector 13) and 16-ID-B of HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoi-lEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415), and Department of Energy-GeoSciences (DE-FG02-94ER14466). HPCAT operations are supported by DOE-NNSA’s Office of Experimental Sciences. Use of the COMPRES-GSECARS gas loading system and PX2 was supported by COMPRES under NSF Cooperative Agreement EAR-1661511, and by GSECARS through NSF grant EAR-1634415 and DOE grant DE-FG02-94ER14466. Work at Argonne (sample preparation, characterization, and crystal growth) is supported by the U.S. DOE, Office of Basic Energy Science, Materials Science and Engineering Division. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This work at University of Utah was supported by the U.S. Department of Energy, Office of Science, Fusion Energy Sciences under Award Number DE-SC0020340 (S.D.). DFT calculations at Northwestern University acknowledge National Science Foundation through the MRSEC program (NSF-DMR 1720139) at the Materials Research Center. The authors acknowledge the computing resources provided by the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. Publisher Copyright: © 2021, The Author(s).

PY - 2021/12/1

Y1 - 2021/12/1

N2 - Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase I213 to R3 induced by pressure in two isostructural defect antiperovskites Hg3Te2Cl2 (15.5 GPa) and Hg3Te2Br2 (17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ4, similar to the archetypal ferroelectric material BaTiO3 at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg3Te2Br2 with an unexpectedly stable R3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems.

AB - Ferroelectricity is typically suppressed under hydrostatic compression because the short-range repulsions, which favor the nonpolar phase, increase more rapidly than the long-range interactions, which prefer the ferroelectric phase. Here, based on single-crystal X-ray diffraction and density-functional theory, we provide evidence of a ferroelectric-like transition from phase I213 to R3 induced by pressure in two isostructural defect antiperovskites Hg3Te2Cl2 (15.5 GPa) and Hg3Te2Br2 (17.5 GPa). First-principles calculations show that this transition is attributed to pressure-induced softening of the infrared phonon mode Γ4, similar to the archetypal ferroelectric material BaTiO3 at ambient pressure. Additionally, we observe a gradual band-gap closing from ~2.5 eV to metallic-like state of Hg3Te2Br2 with an unexpectedly stable R3 phase even after semiconductor-to-metal transition. This study demonstrates the possibility of emergence of polar metal under pressure in this class of materials and establishes the possibility of pressure-induced ferroelectric-like transition in perovskite-related systems.

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JF - Nature Communications

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Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg₃Te₂X₂ (X = Cl, Br)

Abstract

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CSD 2021961: Experimental Crystal Structure Determination

CSD 2021973: Experimental Crystal Structure Determination

CSD 2021972: Experimental Crystal Structure Determination

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Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br)

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CSD 2021961: Experimental Crystal Structure Determination

CSD 2021973: Experimental Crystal Structure Determination

CSD 2021972: Experimental Crystal Structure Determination

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Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg₃Te₂X₂ (X = Cl, Br)