Designing Polar Covalent Hybrid Cadmium-Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double-Site Dual FBUs Tailoring

IF 12.1 2区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Small Pub Date : 2025-01-26 DOI:10.1002/smll.202412173

Yi-Fan Fu, Wen-Dong Yao, Jiajing Wu, Qiao-Feng Huang, Yu-Mei Zhang, Wenfeng Zhou, Wenlong Liu, Sheng-Ping Guo

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Abstract

The pressing demand for both established and innovative technologies to expand laser wavelengths has rendered high-performance nonlinear optical (NLO) crystals with large optical anisotropy indispensable. Here, centrosymmetric [SHC(NH₂)₂]₂CdBr₄ (1) and pseudo-2D layered [SC(NH₂)₂]₂CdBr₂ (2), as well as pseudo-3D noncentrosymmetric [SC(NH₂)₂]₂CdCl₂ (3) are successfully synthesized through the introduction of π-conjugated SC(NH₂)₂ groups. Compared to ionic compound 1 containing full-halogen coordination tetrahedra, covalent compounds 2 and 3 featuring novel polar [SC(NH₂)₂]₂CdX₂ (X = Br, Cl) tetrahedral units demonstrate enhanced bandgaps (>4 eV) and birefringences (>0.3@546 nm) due to the unique coordination environment. Remarkably, 3 exhibits a strong second-harmonic generation (SHG) response (2.1 × KH₂PO₄(KDP)), high laser-induced damage thresholds (30 × AgGaS₂(AGS), and excellent water stability. The birefringence of 3 is the largest among the hybrid halides NLO crystals containing d¹⁰ metal cations. Detailed theoretical calculations confirm that such a modified double-site dual functional building units (FBUs) substitution is an effective strategy for designing superior optical materials with large birefringence and strong SHG response, paving the way for the development of high-performance devices in related fields.

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通过双位点双 FBUs 裁剪设计具有强光学各向异性的极性共价杂化镉基卤化物紫外非线性光学晶体

现有的和创新的技术对扩大激光波长的迫切需求使得具有大光学各向异性的高性能非线性光学晶体（NLO）必不可少。本文通过引入π共轭的SC(NH2)2基团，成功合成了中心对称的[SHC(NH2)2]2CdBr4(1)和伪二维层状的[SC(NH2)2]2CdBr2(2)，以及伪三维非中心对称的[SC(NH2)2]2CdCl2(3)。与含有全卤素配位四面体的离子化合物1相比，具有新型极性[SC(NH2)2]2CdX2 （X = Br, Cl）四面体单元的共价化合物2和3由于独特的配位环境，具有增强的带隙（>4 eV）和双折射（>0.3@546 nm）。值得注意的是，3具有强的二次谐波产生（SHG）响应（2.1 × KH2PO4(KDP)），高激光诱导损伤阈值（30 × AgGaS2(AGS)）和优异的水稳定性。在含d10金属阳离子的杂化卤化物NLO晶体中，3的双折射最大。详细的理论计算证实，这种改进的双位置双功能建筑单元（FBUs）替代是设计具有大双折射和强SHG响应的优质光学材料的有效策略，为相关领域高性能器件的发展铺平了道路。

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来源期刊

Small 工程技术-材料科学：综合

CiteScore

17.70

自引率

3.80%

发文量

1830

审稿时长

2.1 months

期刊介绍： Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments. With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology. Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.