Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra

Chao Wu; Tianhui Wu; Xingxing Jiang; Zujian Wang; Hongyuan Sha; Lin Lin; Zheshuai Lin; Zhipeng Huang; Xifa Long; Mark G. Humphrey; Chi Zhang

doi:10.1021/jacs.1c00416

Large Second-Harmonic Response and Giant Birefringence of CeF₂(SO₄) Induced by Highly Polarizable Polyhedra

Chao Wu, Tianhui Wu, Xingxing Jiang, Zujian Wang, Hongyuan Sha, Lin Lin, Zheshuai Lin, Zhipeng Huang, Xifa Long, Mark G. Humphrey, Chi Zhang^*

^*Corresponding author for this work

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

150 Citations (Scopus)

Abstract

Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.

Original language	English
Pages (from-to)	4138-4142
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	143
Issue number	11
DOIs	https://doi.org/10.1021/jacs.1c00416
Publication status	Published - 24 Mar 2021

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title = "Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra",

abstract = "Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.",

author = "Chao Wu and Tianhui Wu and Xingxing Jiang and Zujian Wang and Hongyuan Sha and Lin Lin and Zheshuai Lin and Zhipeng Huang and Xifa Long and Humphrey, {Mark G.} and Chi Zhang",

year = "2021",

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T1 - Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra

AU - Wu, Chao

AU - Wu, Tianhui

AU - Jiang, Xingxing

AU - Wang, Zujian

AU - Sha, Hongyuan

AU - Lin, Lin

AU - Lin, Zheshuai

AU - Huang, Zhipeng

AU - Long, Xifa

AU - Humphrey, Mark G.

AU - Zhang, Chi

PY - 2021/3/24

Y1 - 2021/3/24

N2 - Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.

AB - Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.

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Large Second-Harmonic Response and Giant Birefringence of CeF₂(SO₄) Induced by Highly Polarizable Polyhedra

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