Multifunctional Cu2TSiS4 (T = Mn and Fe): Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties

Zachary T. Messegee; Jun Sang Cho; Andrew J. Craig; V. Ovidiu Garlea; Yan Xin; Chang Jong Kang; Thomas E. Proffen; Hari Bhandari; Jordan C. Kelly; Nirmal J. Ghimire; Jennifer A. Aitken; Joon I. Jang; Xiaoyan Tan

doi:10.1021/acs.inorgchem.2c03754

Multifunctional Cu₂TSiS₄ (T = Mn and Fe): Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties

Zachary T. Messegee, Jun Sang Cho, Andrew J. Craig, V. Ovidiu Garlea, Yan Xin, Chang Jong Kang, Thomas E. Proffen, Hari Bhandari, Jordan C. Kelly, Nirmal J. Ghimire, Jennifer A. Aitken, Joon I. Jang, Xiaoyan Tan

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Abstract

Cu₂TSiS₄ (T = Mn and Fe) polycrystalline and single-crystal materials were prepared with high-temperature solid-state and chemical vapor transport methods, respectively. The polar crystal structure (space group Pmn2₁) consists of chains of corner-sharing and distorted CuS₄, Mn/FeS₄, and SiS₄ tetrahedra, which is confirmed by Rietveld refinement using neutron powder diffraction data, X-ray single-crystal refinement, electron diffraction, energy-dispersive X-ray spectroscopy, and second harmonic generation (SHG) techniques. Magnetic measurements indicate that both compounds order antiferromagnetically at 8 and 14 K, respectively, which is supported by the temperature-dependent (100-2 K) neutron powder diffraction data. Additional magnetic reflections observed at 2 K can be modeled by magnetic propagation vectors k = (1/2,0,1/2) and k = (1/2,1/2,1/2) for Cu₂MnSiS₄ and Cu₂FeSiS₄, respectively. The refined antiferromagnetic structure reveals that the Mn/Fe spins are canted away from the ac plane by about 14°, with the total magnetic moments of Mn and Fe being 4.1(1) and 2.9(1) μ_B, respectively. Both compounds exhibit an SHG response with relatively modest second-order nonlinear susceptibilities. Density functional theory calculations are used to describe the electronic band structures.

Original language	English
Pages (from-to)	530-542
Number of pages	13
Journal	Inorganic Chemistry
Volume	62
Issue number	1
DOIs	https://doi.org/10.1021/acs.inorgchem.2c03754
State	Published - Jan 9 2023

Funding

Z.T.M. and X.T. were supported by start-up funding from George Mason University. J.A.A. and A.J.C. recognize funding provided by the United States National Science Foundation, DMR-1611198. J.I.J. acknowledges support from the Basic Science Research Programs (2021R1A2C2013625) through the National Research Foundation of Korea (NRF), funded by the Korean government. Special thanks to G&H Cleveland for donating the optical-grade AGS and AGSe reference materials that were used for NLO studies. N.J.G. acknowledges the support from the National Science Foundation (NSF) CAREER award DMR-2143903. Magnetic measurements at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. C.J.K. was supported by the NRF grant (NRF-2022R1C1C1008200). This work used resources at the Spallation Neutron Source, DOE Office of Science Facilities operated by the Oak Ridge National Laboratory. TEM work was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative agreement no. DMR-1644779 and the State of Florida. We thank Dr. Thomas J. Emge (Rutgers, The State University of New Jersey) for helping with single-crystal refinements.

Funders	Funder number
Basic Science Research Programs	2021R1A2C2013625
State University of New Jersey
State of Florida
National Science Foundation	DMR-1611198, DMR-2143903
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
George Mason University
Division of Materials Sciences and Engineering	DMR-1644779, NRF-2022R1C1C1008200
National Research Foundation of Korea

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10.1021/acs.inorgchem.2c03754

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Messegee, Z. T., Cho, J. S., Craig, A. J., Garlea, V. O., Xin, Y., Kang, C. J., Proffen, T. E., Bhandari, H., Kelly, J. C., Ghimire, N. J., Aitken, J. A., Jang, J. I., & Tan, X. (2023). Multifunctional Cu₂TSiS₄ (T = Mn and Fe): Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties. Inorganic Chemistry, 62(1), 530-542. https://doi.org/10.1021/acs.inorgchem.2c03754

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title = "Multifunctional Cu2TSiS4 (T = Mn and Fe): Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties",

abstract = "Cu2TSiS4 (T = Mn and Fe) polycrystalline and single-crystal materials were prepared with high-temperature solid-state and chemical vapor transport methods, respectively. The polar crystal structure (space group Pmn21) consists of chains of corner-sharing and distorted CuS4, Mn/FeS4, and SiS4 tetrahedra, which is confirmed by Rietveld refinement using neutron powder diffraction data, X-ray single-crystal refinement, electron diffraction, energy-dispersive X-ray spectroscopy, and second harmonic generation (SHG) techniques. Magnetic measurements indicate that both compounds order antiferromagnetically at 8 and 14 K, respectively, which is supported by the temperature-dependent (100-2 K) neutron powder diffraction data. Additional magnetic reflections observed at 2 K can be modeled by magnetic propagation vectors k = (1/2,0,1/2) and k = (1/2,1/2,1/2) for Cu2MnSiS4 and Cu2FeSiS4, respectively. The refined antiferromagnetic structure reveals that the Mn/Fe spins are canted away from the ac plane by about 14°, with the total magnetic moments of Mn and Fe being 4.1(1) and 2.9(1) μB, respectively. Both compounds exhibit an SHG response with relatively modest second-order nonlinear susceptibilities. Density functional theory calculations are used to describe the electronic band structures.",

author = "Messegee, {Zachary T.} and Cho, {Jun Sang} and Craig, {Andrew J.} and Garlea, {V. Ovidiu} and Yan Xin and Kang, {Chang Jong} and Proffen, {Thomas E.} and Hari Bhandari and Kelly, {Jordan C.} and Ghimire, {Nirmal J.} and Aitken, {Jennifer A.} and Jang, {Joon I.} and Xiaoyan Tan",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

year = "2023",

month = jan,

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doi = "10.1021/acs.inorgchem.2c03754",

language = "English",

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T1 - Multifunctional Cu2TSiS4 (T = Mn and Fe)

T2 - Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties

AU - Messegee, Zachary T.

AU - Cho, Jun Sang

AU - Craig, Andrew J.

AU - Garlea, V. Ovidiu

AU - Xin, Yan

AU - Kang, Chang Jong

AU - Proffen, Thomas E.

AU - Bhandari, Hari

AU - Kelly, Jordan C.

AU - Ghimire, Nirmal J.

AU - Aitken, Jennifer A.

AU - Jang, Joon I.

AU - Tan, Xiaoyan

PY - 2023/1/9

Y1 - 2023/1/9

N2 - Cu2TSiS4 (T = Mn and Fe) polycrystalline and single-crystal materials were prepared with high-temperature solid-state and chemical vapor transport methods, respectively. The polar crystal structure (space group Pmn21) consists of chains of corner-sharing and distorted CuS4, Mn/FeS4, and SiS4 tetrahedra, which is confirmed by Rietveld refinement using neutron powder diffraction data, X-ray single-crystal refinement, electron diffraction, energy-dispersive X-ray spectroscopy, and second harmonic generation (SHG) techniques. Magnetic measurements indicate that both compounds order antiferromagnetically at 8 and 14 K, respectively, which is supported by the temperature-dependent (100-2 K) neutron powder diffraction data. Additional magnetic reflections observed at 2 K can be modeled by magnetic propagation vectors k = (1/2,0,1/2) and k = (1/2,1/2,1/2) for Cu2MnSiS4 and Cu2FeSiS4, respectively. The refined antiferromagnetic structure reveals that the Mn/Fe spins are canted away from the ac plane by about 14°, with the total magnetic moments of Mn and Fe being 4.1(1) and 2.9(1) μB, respectively. Both compounds exhibit an SHG response with relatively modest second-order nonlinear susceptibilities. Density functional theory calculations are used to describe the electronic band structures.

AB - Cu2TSiS4 (T = Mn and Fe) polycrystalline and single-crystal materials were prepared with high-temperature solid-state and chemical vapor transport methods, respectively. The polar crystal structure (space group Pmn21) consists of chains of corner-sharing and distorted CuS4, Mn/FeS4, and SiS4 tetrahedra, which is confirmed by Rietveld refinement using neutron powder diffraction data, X-ray single-crystal refinement, electron diffraction, energy-dispersive X-ray spectroscopy, and second harmonic generation (SHG) techniques. Magnetic measurements indicate that both compounds order antiferromagnetically at 8 and 14 K, respectively, which is supported by the temperature-dependent (100-2 K) neutron powder diffraction data. Additional magnetic reflections observed at 2 K can be modeled by magnetic propagation vectors k = (1/2,0,1/2) and k = (1/2,1/2,1/2) for Cu2MnSiS4 and Cu2FeSiS4, respectively. The refined antiferromagnetic structure reveals that the Mn/Fe spins are canted away from the ac plane by about 14°, with the total magnetic moments of Mn and Fe being 4.1(1) and 2.9(1) μB, respectively. Both compounds exhibit an SHG response with relatively modest second-order nonlinear susceptibilities. Density functional theory calculations are used to describe the electronic band structures.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 1

ER -

Multifunctional Cu₂TSiS₄ (T = Mn and Fe): Polar Semiconducting Antiferromagnets with Nonlinear Optical Properties

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