CsLiB_6O_(10)晶体及熔体微结构的高温拉曼光谱研究  

High Temperature Raman Spectroscopic Study on the Micro-structures of CsLiB_6O_(10) Crystal and Its Melt

作　　者：王静[1] 尤静林[1] 王媛媛[1] 张国春[2] 万松明[3] 傅佩珍[2] 殷绍唐[3] 刘钦[1] 王晨阳[1] 刘晓伟[1] 

机构地区：[1]上海大学上海市现代冶金及材料制备重点实验室,上海200072 [2]中国科学院北京理化技术研究所北京人工晶体研究发展中心,北京100190 [3]中国科学院安徽光学精密研究所,安徽省光子器件与材料重点实验室,合肥230031

出　　处：《人工晶体学报》2013年第3期397-401,共5页Journal of Synthetic Crystals

基　　金：国家自然科学基金重点项目(50932005);国家自然科学基金(20973107;40973046);上海市科委国际合作项目(12520709200)

摘　　要：本文利用高温原位拉曼光谱技术,测定了非线性光学晶体硼酸铯锂(CsLiB6O10,CLBO)晶体及其熔体的变温拉曼光谱。利用密度泛函理论计算了基本单元为(B3O7)5-六元环的CLBO晶体的拉曼光谱,并对振动模式进行了分析归属。在升温过程中,CLBO晶体的拉曼光谱出现展宽和红移,无相变发生;在熔化过程中,CLBO晶体微结构中(B3O7)5-六元环的[BO4]四面体发生异构化反应,转变为[BO3]三角形,即晶体相中的(B3O7)5-环变为熔体中的(B3O6)3-环。利用量子化学从头计算方法计算分析了熔体中结构基元的拉曼光谱谱学特征,结合熔体实测结果,表明CLBO熔体的阴离子基元为四个(B3O6)3-六元环组成的大四元环超级结构。Temperature dependent Raman spectra of the nonlinear optical crystal, CsLiBrOlo （CLBO） and its melt were recorded by in situ high temperature Raman spectroscopic technique. The vibrational modes of the CLBO crystal with （B3O7 ）5- ring as basic unit were simulated and assigned by density functional theory（DFF） method. As the temperature increasing, nearly all of the peaks of CLBO crystal broadened and decreased in wavenumber, without phase transition. An isomerization reaction from [ BO4 ] tetrahedron to [ BO3 ] triangle occurred during the melting process, that is, （B3O7 ）5- in CLBO crystal structure translated into （B3O6） 3- groups in CLBO melt. The spectroscopy characteristics of the Raman spectrum of structure unit in melt were caculated by quantum chemistry ab initio. It can be concluded that there exists super ring structure which contains four （ B3O6 ） 3 - rings connected by each other, which agreed well with the experimental result.

关 键 词：CsLiB6O10晶体 高温拉曼光谱 熔体结构 晶体生长 

分 类 号：O781[理学—晶体学]