Rb2MGe3S8 (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe3S8]2- Unit※

doi:10.6023/A22010020

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (5): 633-639.DOI: 10.6023/A22010020 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

Rb₂MGe₃S₈ (M=Zn, Cd): [MGe₃S₈]^2–单元构型变换导致化合物从中心到非心的转变^※

柴贤丹^a^,^b, 陈文发^b, 闫秋楠^b, 刘彬文^b, 姜小明^b^,^*(), 郭国聪^b^,^*()

a 福建师范大学化学与材料学院福州 350007
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350608

投稿日期:2022-01-12 发布日期:2022-02-17
通讯作者: 姜小明, 郭国聪
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(22075283); 国家自然科学基金(22175172); 国家自然科学基金(92161125); 中国科学院青年创新促进会(2020303); 中国科学院青年创新促进会(2021300)

Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※

Xiandan Chai^a^,^b, Wenfa Chen^b, Qiunan Yan^b, Binwen Liu^b, Xiaoming Jiang^b(), Guocong Guo^b()

a School of Chemistry and Materials, Fujian Normal University, Fuzhou, 350007
b State Key Laboratory of Structural Chemistry, Fujian Institute ofResearch on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350608

Received:2022-01-12 Published:2022-02-17
Contact: Xiaoming Jiang, Guocong Guo
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(22075283); National Natural Science Foundation of China(22175172); National Natural Science Foundation of China(92161125); Youth Innovation Promotion Association of Chinese Academy of Sciences(2020303); Youth Innovation Promotion Association of Chinese Academy of Sciences(2021300)

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Abstract

Infrared nonlinear (IR NLO) optical crystals have an essential position in military and civilian fields because of their ability to convert lasers from near infrared (NIR) to mid/far infrared (MIR/FIR). In this work, two alkali-metal chalcogenides, Rb₂MGe₃S₈[M=Zn (1), Cd (2)], were successfully synthesized by high-temperature solid-state reactions. Both compounds feature a two-dimensional layered structure and have a large optical band-gap, the experimental band-gap of 1 and 2 are 3.24 eV and 3.16 eV, respectively. Compound 1 belongs to the centrosymmetric group P-1, while 2 belongs to the non-centrosymmetric space group P2(1)2(1)2(1) and exhibits obvious NLO effect, which is comparable to that of KH₂PO₄ (KDP) (@1064 nm) at the particle size of 50~75 μm. Particle-size dependent NLO response measurements indicated that 2 is non-phase-matchable. Compound 2 exhibits a high laser-induced damage threshold of 16.6×AGS at 1064 nm. Through the analysis of the crystal structures of these two compounds, the reason why their formulas have the same stoichiometric ratio but symmetries are different is the structure change of basic building unit [MGe₃S₈]^2– in 1 and 2. All M atoms in both compounds are coordinated by four S atoms to form MS₄ tetrahedra. In each [CdGe₃S₈]^2–unit of 2, three S atoms bonded to the Cd atom are also bonded to all Ge atoms in that unit, that is to say, each CdS₄ tetrahedron is connected to the other three GeS₄ tetrahedra by sharing S vertices. Unlike the coordination manner in the [CdGe₃S₈]^2– unit of 2, there are only two S atoms bonded to both Zn and Ge atoms in [ZnGe₃S₈]^2–unit of 1. This structure change of [MGe₃S₈]^2– unit eventually led to the non-centrosymmetric transformation. What’s more, to get insight into the origin of NLO effect of 2, theoretical calculations of electronic band structure and NLO susceptibility were performed based on density functional theory.

Key words: chalcogenides, nonlinear optical, non-centrosymmetric transformation, theoretical calculation

Cite this article

Xiandan Chai, Wenfa Chen, Qiunan Yan, Binwen Liu, Xiaoming Jiang, Guocong Guo. Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※[J]. Acta Chimica Sinica, 2022, 80(5): 633-639.

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Fig. & Tab. 8

Figure 1. Simulated and experimental powder XRD patterns of 1 (a) and 2 (b) (the intensities of some peaks on the experimental patterns are significantly different from those on the simulated patterns due to the preferred orientation of the sample, which usually exists in compounds with layered structures)

Empirical formula	Rb₂ZnGe₃S₈
F_w	1369.31
Temperature/K	293(2)
Space group	P-1
a/nm	0.71792(4)
b/nm	0.74790(4)
c/nm	1.44305(7)
α/(°)	88.774(4)
β/(°)	84.409(4)
γ/(°)	72.211(5)
Volume/nm³	0.73424(7)
Z	2
D_calc/(g•cm^–3)	3.214
μ/mm^–1	15.378
GOF on F²	1.037
R₁^a [I≥2σ(I)]	0.0450
wR₂^b [I≥2σ(I)]	0.1142
R₁^a [all data]	0.0649
wR₂^b [all data]	0.1230
(Δρ_max/Δρ_min)/(e•nm^–3)	1080/–1160

Table 1. Crystal data and structure refinement parameters of 1

Empirical formula	Rb₂CdGe₃S₈
F_w	1515.18
Temperature/K	293(2)
Space group	P2(1)2(1)2(1)
a/nm	0.73459(2)
b/nm	1.22234(4)
c/nm	1.69163(7)
α/(°)	90
β/(°)	90
γ/(°)	90
Volume/nm³	1.51895(9)
Z	2
D_calc/(g•cm^–3)	3.313
μ/mm^–1	14.688
GOF on F²	1.002
R₁^a [I≥2σ(I)]	0.0310
wR₂^b [I≥2σ(I)]	0.0644
R₁^a [all data]	0.0400
wR₂^b [all data]	0.0671
Flack	0.988(14)
(Δρ_max/Δρ_min)/(e•nm^–3)	790/–960

Table 2. Crystal data and structure refinement parameters of 2

Figure 2. IR spectra of 1 (a) and 2 (b), absorption spectra of 1 (c) and 2 (d) converted from diffuse reflectance spectra

Figure 3. (a) SHG intensities of 2 and KDP at the particle size of 50~75 μm at incident wavelength of 1.06 μm laser; (b) particle size dependence of SHG intensities of 2 and the reference KDP

Figure 4. (a) A [ZnGe3S8]2– layer of 1 viewed down the a-direction. (b) A [ZnGe3S8]2– layer of 1 viewed down the b-direction. (c) A [ZnGe3S8]2– unit in 1. (d) A [CdGe3S8]2– layer of 2 viewed down the c-direction. (e) A [CdGe3S8]2– layer of 2 viewed down the b-direction. (f) A [CdGe3S8]2– unit in 2

Figure 5. Calculated SHG coefficient tensors d14 (a), effective SHG coefficient deff (b), the energy-dependent birefringence (c) and phase-matching curves (d) of 2

Figure 6. Electronic band structure of 1 (a) and 2 (b); total and partial density of states of 1 (c) and 2 (d)

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Rb₂MGe₃S₈ (M=Zn, Cd): [MGe₃S₈]^2–单元构型变换导致化合物从中心到非心的转变^※

Rb₂MGe₃S₈ (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe₃S₈]^2- Unit^※

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