Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30（M= Ca and Ba, RE= La and Bi）  

新的非线性光学材料K7MRE2B15O30（M=Ca andBa,RE=La and Bi）的合成、表征和理论分析（英文）

作　　者：Zhiqing Xie Ying Wang Shichao Cheng Guopeng Han Zhihua Yang Shilie Pan 解植擎;王颖;程世超;韩国鹏;杨志华;潘世烈(CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS,Xinjiang Key Laboratory of Electronic Information Materials and Devices, Urumqi 830011, China;Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China)

机构地区：[1]CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS,Xinjiang Key Laboratory of Electronic Information Materials and Devices, Urumqi 830011, China [2]Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

出　　处：《Science China Materials》2019年第8期1151-1161,共11页中国科学（材料科学（英文版）

基　　金：supported by the West Light Foundation of the CAS(2016-YJRC-2 and 2015 XBQN-B-11);the National Natural Science Foundation of China(51602341 and 91622107);the Natural Science Foundation of Xinjiang(2016D01B061);Tianshan Innovation Team Program(2018D14001);Key research project of Frontier Science of CAS(QYZDB-SSW-JSC049)

摘　　要：Three new complex borate compounds K7CaBi2B15O30, K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space group R32, while K7BaBi2B15O30 crystallizes in the noncentrosymmetric orthorhombic polar space group Pca21. All of the title compounds have similar three-dimensional crystal structures, which are composed of isolated B5 O10 groups and LaO6 or BiO6 octahedra, and K^+, Ca^2+, and Ba^2+ cations fill into the cavities to keep charge balance. Based on our research, in the system of K7 MIIRE2 B15O30(MII= Ca, Sr,Ba, Zn, Cd, Pb, K/RE0.5;RE = Sc, Y, La, Gd, Lu, Bi),K7BaBi2B15O30 is unique and crystallizes in a different space group, which enriches the structural chemistry of borate.Detailed structural analyses indicate that the structural variation is due to the difference in size and coordination number of the alkaline-earth metal cations. Besides, UV-Vis-NIR spectroscopy analysis and the second-harmonic generation(SHG) measurement on the powder samples show that K7CaBi2B15O30 exhibits a UV cutoff edge(about 282 nm) and a moderate SHG response(about 0.6 × KDP). In addition,thermal analysis and infrared spectroscopy were also presented. To better understand the structure-property relationships of the title compounds, the first-principles calculations have been performed.本文采用高温熔液法合成了三种新型复合硼酸盐化合物K7CaBi2B15O30、K7CaLa2B15O30和K7BaBi2B15O30. K7CaLa2B15O30和K7CaBi2B15O30结晶于三方手性空间群R32中,K7BaBi2B15O30结晶于非中心对称正交极性空间群Pca21.这三个化合物具有相似的三维晶体结构,由孤立的B5O10基团和LaO6或BiO6八面体组成,K^+、Ca^2+、Ba^2+阳离子填充于空隙中以保持电荷平衡.根据我们的调研,在K7MⅡRE2B15O30体系内(MⅡ=Ca,Sr,Ba,Zn,Cd,Pb,K/RE0.5;RE=Sc,Y,La,Gd,Lu,Bi),K7BaBi2B15O30是唯一一个结晶于不同空间群的化合物,其丰富了硼酸盐的结构化学.详细的结构分析表明,碱土金属阳离子的尺寸和配位数的差异是导致结构变化的主要原因.此外,UVVis-NIR光谱分析和倍频效应(SHG)测试表明K7CaBi2B15O30具有较短的截止边(大约282 nm)和适中的倍频效应(约0.6×KDP).我们还进行了热重差热和红外光谱的测试.为了更好地理解上述化合物的结构性能关系,我们还进行了第一性原理计算.

关 键 词：BORATE nonlinear optical materials SHG response structure-properties relationship 

分 类 号：TB34[一般工业技术—材料科学与工程] O611.4[理学—无机化学]