XJIPC OpenIR  > 材料物理与化学研究室
Thesis Advisor潘世烈
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Name硕士
Degree Discipline材料物理与化学
Keyword非线性光学材料 硼酸盐 铌酸盐 单晶结构 相匹配

硼酸盐因其优异的非线性光学性能而被广泛的研究,因此近些年来,硼化合物无机材料的研究与应用得到了迅速发展,出现了一系列性能优异的晶体材料。除此之外,由于碱金属和碱土金属原子结构有利于紫外光的透过,因此碱金属碱土金属复合硼酸盐常常用作合成紫外非线性光学晶体。 本论文通过室温溶液法成功的合成了两种碱金属碱土金属复合硼酸盐,Rb2Ca[B4O5(OH)4]2·8H2O(RCBO)和K2Ca[B4O5(OH)4]2·8H2O(KCBO)晶体,并且分别得到了尺寸为8 × 5 × 3 mm3和11 × 6 × 5 mm3的单晶。这两种化合物结构是同构的,都属于正交晶系,P212121空间群,该分子中含有八个结晶水,两个[B4O5(OH)4]2-基团,一个7配位的钙离子和配位数分别为7和9的两个钾(铷)离子,整个分子呈三维网状结构,RCBO和KCBO的倍频效应分别是0.5倍和0.3倍的KH2PO4 (KDP),晶体的透过光谱表明这两个晶体的紫外截止边都在200nm左右。 铌酸盐体系中的非线性光学晶体因具有较大的非线性光学系数而受到广泛的关注,本文以生长具有大的倍频效应的晶体为出发点,在K-Nb-Si-O体系中选择K3Nb3O6Si2O7(KNSO)化合物进行生长,研究了适合KNSO晶体生长的助熔剂体系,确定了以H3BO3+LiF为助熔剂的实验方法,采用高温溶液法生长出了7 × 3 × 3 mm3 的KNSO晶体,并对其进行了倍频测试,结果表明该化合物有非常大的倍频效应,约为6倍的KDP,通过Kurtz法表明该化合物可以实现相匹配。

Other Abstract

Borates have been the focus of intense research as second order nonlinear optical (NLO) materials since the discovery of their excellent NLO properties and potential applications.Various cations including alkali and alkaline earth have been employed to synthesize novel UV borate NLO materials. In our study, two borate NLO materials, Rb2Ca[B4O5(OH)4]2·8H2O(RCBO) and K2Ca[B4O5(OH)4]2·8H2O(KCBO) have been prepared through slow evaporation at room temperature with size as 8 × 5 × 3 mm3 and 11 × 6 × 5 mm3 respectively. Single-crystal X-ray diffraction data reveal that RCBO and KCBO are isostructural and noncentrosymmetric. They crystallize in the orthorhombic system, space group P212121. RCBO (KCBO) consists of RbO7 (KO7) polyhedra, RbO9 (KO9) polyhedra, CaO7 polyhedra, [B4O5(OH)4]2- polyborate anions, and H2O molecules. The molecular has a three-dimensional network structure. RCBO and KCBO produce second harmonic generation (SHG) intensities of 0.5 × KDP and 0.3 × KDP, respectively, and they are both phase-matchable. The transmission spectra of these compounds indicate that the UV absorption cutoff edges at 200nm. Niobate have been widespread concerned because of their large nonlinear optical coefficients. In our study, we aim at the crystal with large nonlinear optical coefficients, so we choose K3Nb3O6Si2O7 (KNSO) compound from K-Nb-Si-O system as our final research object. We discussed the flux system and found that the H3BO3+LiF flux system is suitable for growth of KNSO crystal. Its single crystals have been grown with sizes up to 7 × 3 × 3 mm3 by the high-temperature techniques. The powder SHG intensity measured by the Kurtz method indicates that KNSO is phase-matchable and its SHG coefficient is 6 times as large as that of KDP.

Document Type学位论文
Recommended Citation
GB/T 7714
罗将. 非线性光学材料八水合硼酸钙铷(钾)和钾铌硅氧的研究[D]. 北京. 中国科学院研究生院,2011.
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