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基于平面MO3基团的新型紫外无机光学晶体的设计组装及性能研究
刘莉莉
学位类型博士
导师潘世烈
2017-05-31
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料物理化学
关键词双折射晶体 硼酸盐 碳酸盐 硝酸盐
摘要

本论文以设计合成新型紫外/深紫外光学晶体材料为目标,选用具有共轭π键的MO3 (M=B、C、N)基团、聚合B-O基团、卤素、具有二阶姜-泰勒畸变的阳离子、碱金属/碱土金属等不同的功能基元进行设计组装和结构优化。采用传统的高温熔液法或水热法,成功地得到了20余种新的硼酸盐,碳酸盐,硝酸盐,以及复合阴离子化合物。通过探索和优化晶体的生长条件,成功地将设计合成的多种化合物生长出了毫米级晶体,并对其性能进行了初步研究。研究表明:在合成的20余种化合物中,7种具有非中心对称结构,4种在紫外/深紫外光学材料方面具有潜在应用前景。1. 基于平面BO3基团的晶体设计及性能表征根据阴离子基团理论,含共轭π键的BO3基团具有较大的各向异性极化率和二阶非线性光学系数,因此有利于产生较大的双折射率和非线性光学效应。在该部分,通过提高硼酸盐框架中阳离子所占比例,设计合成仅含孤立的BO3基元的硼酸盐化合物。对于阳离子,我们选用可拓展紫外截止边的碱金属或碱土金属,或具有姜-泰勒畸变的阳离子多面体,最终我们得到了K5Ba10(BO3)8F和Pb2Bi2GaB3O11两个化合物,它们都是相应体系中首次出现的化合物。尤其是Pb2Bi2GaB3O11,根据第一性原理计算,它在可见光区域具有较大的双折射率值(0.07@589 nm),这归因于结构中Bi3+和Pb2+离子的立构活性孤对电子的作用,以及孤立的BO3基团的贡献。此外,Pb2Bi2GaB3O11是同成分熔融化合物,可以通过提拉法进行大尺寸晶体的生长,并进一步分析其光学性能。2. 基于平面CO3构型的晶体设计及性能表征CO3与BO3具有相似的空间构型,同样有利于产生较大的双折射率和倍频效应,因此对碳酸盐的研究可以拓宽紫外光学晶体的研究范围。通过在碳酸盐体系中引入不同功能的阳离子以及卤素离子,我们获得了一系列具有新颖结构和优异光学性能的碳酸盐,如Cs3Pb2(CO3)3I、KBa2(CO3)2F、RbBa2(CO3)2F、RbBaCO3F、Rb2Sr2(CO3)3、Rb2Ba2(CO3)3、Cs2Ba2(CO3)3。其中,Cs3Pb2(CO3)3I化合物在可见光区理论计算的双折射率大约为0.09,是一种具有潜在应用价值的双折射晶体。除此之外我们还探讨了卤素离子的位置对CO3基团的排列以及对晶体光学性质的影响。3. 基于平面NO3基团的晶体设计及性能表征同样具有共轭π键的NO3基团研究较少。基于已报道的SrNO3(OH)·H2O和Sr2(OH)3NO3晶体,我们对Sr-NO3-H体系进行了尝试性的探索和研究,并设计合成了该体系的第三个化合物SrNO3(OH)·H2O晶体。理论计算表明,它在1064 nm处的双折射率为0.12,这与a-BaB2O4双折射率相当。除此之外,我们还讨论了Sr-NO3-H体系中阳离子框架对该体系化合物结构和性能的影响。4. 复合阴离子基团化合物的设计合成及性能表征基于前面的实验经验,我们成功地将多种阴离子基团进行了复合,并在结构中引入了大尺寸的卤素离子,从而获得了一系列具有非心结构的化合物,分别是Rb9[B4O5(OH)4]3(CO3)I·7H2O、Rb9[B4O5(OH)4]3(CO3)Cl·7H2O、Rb9[B4O5(OH)4]3(CO3)Br·7H2O、K9[B4O5(OH)4]3(CO3)I·7H2O和K9[B4O5(OH)4]3(CO3)OH·7H2O,我们将该系列简称为A9[B4O5(OH)4]3(CO3)X·7H2O。5. 含聚合B-O基团的硼酸盐的合成及性能表征除了含孤立BO3基团的硼酸盐,在探索MO3基团化合物的过程中,我们还发现了具有聚合B-O基团的化合物。我们在BaO-B2O3体系中发现了Ba2B6O11和Ba2B10O17晶体,它们的发现丰富了BaO-B2O3的家族体系。Ba2B6O11和Ba2B10O17晶体具有新颖的晶体结构和优异的光学性能,尤其是Ba2B10O17晶体,透过光谱表明它的截止边小于180 nm,可应用为深紫外窗口材料。我们在K-B-O-H体系中还发现了K2B4O7·H2O和K2B4O7·3.6H2O两个化合物。通过与已知化合物K2B4O7·2H2O的结构进行比对,我们发现了随着H2O分子含量的增加,K2B4O7·vH2O的对称性以及单胞体积都会发生变化。以复合阴离子化合物A9[B4O5(OH)4]3(CO3)X·7H2O为结构模版,将CO3基团用NaO6八面体替换,得到了NaRb6[B4O5(OH)4]3I和NaRb6[B4O5(OH)4]3OH晶体,成功拓展了晶体的紫外截止边。

其他摘要

The main objective of this thesis is to design and synthesize new UV/deep-UV optical materials. The main synthetic strategy used in the research is to combine different functional units together to explore new compounds with practical properties. The functional units involved contain 1) the π-conjugated planar MO3 (M=B, C, N) triangles, 2) polymerized B-O groups, 3) halide ions, 4) stereochemically active lone pair (SCALP) cations, and 5) alkaline/alkaline-earth metals. Under this strategy, we have successfully synthesized over twenty new compounds, nine of which possess the noncentrosymmetric structures, and four of which are promising UV optical materials.1. The syntheses and characterization of the borates with isolated BO3 triangles.According to Chen’s anion group theory, the BO3 triangles have the π-conjugated configuration and strongly anisotropic polarization, which will be conducive to generate the large SHG (Second Harmonic Generation) response and birefringence. Therefore, the second part of my work is to combine the isolated BO3 triangles with different types of cations to find new compounds. By using this strategy, we have synthesized two compounds, K5Ba10(BO3)8F and Pb2Bi2GaB3O11. The two compounds represent the first compound in their respective system. Especially for Pb2Bi2GaB3O11, the first-principle calculation shows that the calculated birefringence of Pb2Bi2GaB3O11 in visible region is 0.07, which is attributed to the synergistic coordination of SCALP Pb2+ and the π-conjugated BO3 groups. In addition, Pb2Bi2GaB3O11 is a congruent compound, so we can obtain the large-scaled ctrystal of Pb2Bi2GaB3O11 through melt method to further evaluate its optical property.2. The syntheses and characterization of the carbonates with CO3 triangles.Compared with the BO3 unit, the CO3 group has a larger anisotropic susceptibility. Therefore, we start to research the carbonate system, and alkaline metals, alkaline-earth metals and halides are incorporated into the system. And then we successfully synthesized Cs3Pb2(CO3)3I, KBa2(CO3)2F, RbBa2(CO3)2F, RbBaCO3F, Rb2Sr2(CO3)3, Rb2Ba2(CO3)3 and Cs2Ba2(CO3)3. Among these compounds, Cs3Pb2(CO3)3I has a moderate birefringence, which is about 0.09 at 589 nm according to the first-principle calculation. Therefore, Cs3Pb2(CO3)3I may be a potential UV birefringent material. In addition, we also discussed the effect of halides’ position on the arrangement of the CO3 group, which plays an essential role on crystals’ optical properties. 3. The synthesis and characterization of the nitrate with the NO3 triangles. Nitrate compounds also can own excellent optical properties. Based on the reported compound Sr2(OH)3NO3 with excellent optical properties, we decided to research new compounds in Sr-NO3-H system. And then we successfully designed and synthesized a new centrosymmetric compound, SrNO3(OH)·H2O, which has a large birefringence of 0.12 at 1064 nm. After comparing the crystal structures of compounds in Sr-N-O-H system, we found that a tight cationic framework is more conducive to guide anionic groups to arrange in parallel model. 4. Design and syntheses of compounds with multi-anionic groups.Based on the experience of the preceding three experiment processes, we have also successfully combined different anionic groups together to design and synthesize series of new noncentrosymmetric compounds with interesting crystal structures. They are Rb9[B4O5(OH)4]3(CO3)I·7H2O, Rb9[B4O5(OH)4]3(CO3)Cl·7H2O, Rb9[B4O5(OH)4]3(CO3)Br·7H2O, K9[B4O5(OH)4]3(CO3)I·7H2O, and K9[B4O5(OH)4]3(CO3)OH·7H2O, which we can call A9[B4O5(OH)4]3(CO3)X·7H2O. 5. The syntheses and characterization of borates with polyborate anions.During our research, we have also found several new compounds with interesting polyborate anions and excellent optical properties. They consist of two new barium borates Ba2B6O11 and Ba2B10O7 synthesized with high temperature solid state method in the open system. Two tetraborates were found via hydrothermal method, and they are K2B4O7·H2O and K2B4O7·3.6H2O. The symmetry and cell volume of K2B4O7·vH2O are going to be higher and larger, with increasing of the amount of H2O molecules. Through replacing the CO3 groups of A9[B4O5(OH)4]3(CO3)X·7H2O by NO6 octahedra, we synthesized the NaRb6[B4O5(OH)4]3I and NaRb6[B4O5(OH)4]3OH crystals with a chiral space group R32, and the band gap was also broadened.

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4967
专题材料物理与化学研究室
作者单位中国科学院新疆理化技术研究所
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刘莉莉. 基于平面MO3基团的新型紫外无机光学晶体的设计组装及性能研究[D]. 北京. 中国科学院大学,2017.
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