Y2(CO3)3•H2O and (NH4)2Ca2Y4(CO3)9•H2O: Partial Aliovalent Cation Substitution Enabling Evolution from Centrosymmetry to Noncentrosymmetry for Nonlinear Optical Response

被引:29
作者
Peng, Guang [1 ]
Lin, Chen-Sheng [1 ]
Yang, Yi [2 ,3 ]
Zhao, Dan [4 ]
Lin, Zheshuai [2 ]
Ye, Ning [1 ]
Huang, Jin-Shun [1 ]
机构
[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, Key Lab Optoelect Mat Chem & Phys, Fuzhou 350002, Fujian, Peoples R China
[2] Chinese Acad Sci, Tech Inst Phys & Chem, Beijing 100190, Peoples R China
[3] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[4] Henan Polytech Univ, Dept Chem & Phys, Jiaozuo 454000, Henan, Peoples R China
基金
中国国家自然科学基金;
关键词
FLUORIDE CARBONATE; GENERATION; CRYSTALS; BORATE; DESIGN; OXIDE;
D O I
10.1021/acs.chemmater.8b04428
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An effective approach, the partial aliovalent cation substitution (PACS), was successfully employed to develop nonlinear optical (NLO) material. Two novel rare earth carbonates, Y-2(CO3)(3)center dot H2O (YC) and (NH4)(2)Ca2Y4(CO3)(9)center dot H2O (CYC), were synthesized, which feature the same honeycomb-like framework structure. From YC to CYC, the partial substitution of Y3+ with Ca2+ led to the evolution of space group from centrosymmetric P6(3)/mcm to noncentrosymmetric P6(3)mc. The CYC exhibited a second harmonic generation (SHG) effect of 2.1 x KH2PO4 (KDP) and a deep-UV cutoff edge (<200 nm). It was concluded that the SHG effect originates from the ordered arrangement of (CO3)(2-) groups and the dipole polarization enhancement of [Ca0.33Y0.67O9] polyhedra. Specifically, the long-range ordered electric field of channels induced the ordered arrangement of (CO3)(2-) groups. This synthetic approach and SHG-activated induction mechanism may afford new strategies for the design and synthesis of NLO materials.
引用
收藏
页码:52 / 56
页数:5
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