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题名: 基于平面BO3、产业化晶体结构优化及刚性基元的倍频材料设计、合成及性能表征
作者: 俞洪伟
答辩日期: 2014-05-26
导师: 潘世烈
专业: 材料物理与化学
授予单位: 中国科学院大学
授予地点: 北京
学位: 博士
关键词: 非线性光学晶体 ; 硼酸盐 ; 平面构型BO3 ; BBO ; KBBF ; 刚性基团
摘要: 紫外非线性光学晶体作为重要的光电功能材料,对固态激光器输出不同频率激光具有特殊意义。本论文以设计合成新型紫外/深紫外非线性光学材料为目标,采用将平面构型的BO3 与不同类型阳离子进行组合、对产业化硼酸盐晶体进行结构优化及在结构中引入刚性AlO4 等合成策略,通过传统的高温固相反应方法,成功设计合成出26 种新硼酸盐化合物,并通过高温溶液法生长了小尺寸晶体,解析了晶体结构,并对其性能进行了初步研究。研究表明:在合成的26 种硼酸盐中,有9 种具有非中心对称结构,4 种在紫外/深紫外非线性光学材料方面具有潜在应用前景。1. BO3 型硼酸盐化合物的合成和性能表征根据阴离子基团理论,BO3 基团的π 共轭电子结构和强的各向异性极化,有利于材料产生大的非线性光学效应和合适的双折射率。在该部分我们基于阳离子数目效应的理解,在硼酸盐中引入大量阳离子获得了孤立的BO3 结构,并将之与不同类型阳离子进行组合, 成功合成出了包括Pb4O(BO3)2, Pb3Cd3(BO3)4,Pb10Zn8(BO3)12, CsCdBO3 和Li3Ca9(BO3)7·2[LiF]等一系列具有BO3 构型的硼酸盐化合物。其中,Pb4O(BO3)2、CsCdBO3 及Li3Ca9(BO3)7·2[LiF]表现出了非中心对称的晶体结构。并且Pb4O(BO3)2 结构中2 个O 原子不与B 原子配位,为氧合硼酸盐,测试表明该化合物为同成分熔融化合物,粉末倍频效应为3 倍KDP,紫外截止边为280 nm,可见光区计算双折射率为0.04-0.06。CsCdBO3 结晶于立方晶系P213 空间群, 具有较小非线性光学效应且不能实现相位匹配。Li3Ca9(BO3)7·2[LiF],结构中包含有[Li-F]链,可看作离子硼酸盐,其粉末倍频效应约为1 倍KDP,紫外截止边约为230 nm,可见光区计算双折射率约为0.07。2. 基于产业化非线性光学晶体的新材料合成与性能表征β-BBO 和KBBF 是目前世界上已经广泛使用的紫外/深紫外非线性光学晶体,对于β-BBO,相对较长的紫外截止边限制了其在深紫外波段的进一步应用。基于对我们发现的无水碱金属、碱土金属硼酸盐中O/B 比规律的理解,我们使用2个F 原子替代β-BBO 结构中的1 个O 原子有效的调控了β-BBO 晶体中的O/B比,成功的设计合成出了Ba3B6O11F2 化合物,该化合物的B-O 结构为新的B6O14结构基元组成的[B6O11]∞三维网络。由于消除了β-BBO 结构中的终端O 原子,Ba3B6O11F2 的紫外截止边紫移至深紫外(短于190 nm),并且粉末倍频效应测试表明Ba3B6O11F2 化合物粉末倍频效应约为3 倍KDP,可见光区计算双折射率大于0.04,这些性能表明,Ba3B6O11F2 是一种潜在的紫外/深紫外非线性光学材料。KBBF 是在深紫外区具有重要应用的非线性光学晶体材料,并且它也是目前唯一可以通过直接倍频输出波长短于200 nm 的非线性光学材料,但它的层状生长习性和BeO 的剧毒性,限制了它在紫外/深紫外波段的广泛应用,我们使用与Be具有相似化学性质的Zn 替代Be,并且通过强的B-O 键连接相邻的[Zn2BO3O2]层成功合成出了无层状习性的类KBBF 化合物—Cs3Zn6B9O21。测试表明:该化合物紫外截止边为200 nm,可见光区计算双折射率大于0.06,且表现出KBBF族中最大的倍频效应(约3.3 倍KDP)。3. 刚性结构基元对材料结构、性能的影响在硼酸盐中引入刚性的AlO4 基团,我们成功的设计合成出极性的NaBa4(AlB4O9)2Br3 化合物。进一步将结构中刚性AlO4 基团换成BO4 合成出中心结构的NaBa4(B5O9)2F2Cl。将它们的晶体结构和性质与本实验室之前合成出的Cs2SiB4O9 进行比较发现:刚性基元的刚度将极大的影响结构中B-O 基团的畸变程度,大的刚性基团刚度将导致大的B-O 基团畸变,从而导致更大的非线性光学效应,该部分工作将为含刚性基元的新型非线性光学材料设计提供理论指导。4. 其它新化合物合成在实施前三部分的研究中,我们也获得了系列结构新颖的硼酸盐化合物,它们包括开放体系中人工条件下合成的首例硼酸-碳酸混盐化合物:Ba5(BO3)2(CO3)2 和Ba4Sr(BO3)2(CO3)2;系列具有相似计量比,但不完全同构的五硼酸化合物:M3M’B5O10(M= K, Rb;M’=Cd, Zn)和MBaB5O9(M= Na, K);结构包含孤立[B12O24]基团的:Li3KB4O8, LiNa2Sr8B12O24F6Cl, NaCaB2O4F 和Na8Ca7MgB13O27F9四种碱金属、碱土金属复合硼酸盐;以及在具有高粘度的Pb-Zn-B-O 玻璃体系中,首次合成出高B-O 聚合的Pb5Zn4B10O21 化合物,我们对其晶体结构、光学和热学等性质等也进行了系统研究。
英文摘要:
The mainobjective of this dissertation is to design and synthesize new UV and deep-UV nonlinear optical (NLO) borate materials. In the research, some very fruitful strategies have been used. They contain 1) to combine planar BO3 triangles with different types of cations, 2) to improve the properties of industrial borate crystals by changing their structures, and 3) to add the distortion of B-O group by using rigid AlO4 group. Using these strategies, we have successfully synthesized over 20 new borates, nine of which possess the noncentrosymmetric structures, and four of which are promising UV NLO 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 favor the large SHG response and birefringence. Therefore, my first part work is to combine the isolated BO3 triangles with different types of cations. By using this strategy, we have synthesized several borates with isolated BO3 triangles, which consists of Pb4O(BO3)2, Pb3Cd3(BO3)4, Pb10Zn8(BO3)12, CsCdBO3 and Li3Ca9(BO3)7?2[LiF]. Among them, Pb4O(BO3)2, CsCdBO3 and Li3Ca9(BO3)7?2[LiF] crystallize in noncentrosymmetric space groups. For Pb4O(BO3)2, in its crystal structure, two O atoms do not directly connect with B atoms, so it is an oxy-borate compound. And the property characterizations show that Pb4O(BO3)2 melts congruently and possess a SHG response about 3 times of that of KDP, and its UV cut-off edge is about 280 nm. The first-principle calculation shows that the calculated birefringence of Pb4O(BO3)2 is 0.04-0.06 in visible region. For CsCdBO3, it crystallizes in cubic P213 space group and be non-phase matchable. For Li3Ca9(BO3)7?2[LiF], its crystal structure contains the [Li-F] chain resides, so it can be regarded as a LiF salt-inclusion borate. And Li3Ca9(BO3)7?2[LiF] possesses a SHG response similar to that of KDP, wide transparent window with cut-off edge at 230 nm and the moderate calculated birefringence about 0.07 at the visible region. 2. The syntheses and characterization of the compounds based on industrial β-BBO and KBBF: β-BBO and KBBF are both famous borate NLO materials, which have been widely used in the world. However, for β-BBO, its relatively long UV cut-off edge (about 190 nm) limits its further application in deep-UV region. Based on the understanding of rule of the O/B ratio in alkalimetal borate and alkali-earth metal borate, we used two F atoms to substitute one O atom of β-BBO and successfully synthesized Ba3B6O11F2. Its crystal structure is a three-dimensional [B6O11]∞ framework composed of the new B-O building units, [B6O14] groups. Owing to eliminating the terminal O atoms, Ba3B6O11F2 exhibits a wider transparent range than β-BBO. Further, the powder SHG test shows that Ba3B6O11F2 has a SHG response about three times of KDP. The first-principle calculation shows that the calculated birefringence of Ba3B6O11F2 in visible region is about 0.04. Therefore, Ba3B6O11F2 may be a potential UV NLO material. In addition, KBBF is also a famous NLO crystal and it is the only material, which can generate coherent light wavelengths below 200 nm by direct second harmonic generation. However, the strong layer habit and the high toxicity of the beryllium oxide powders make it difficult to grow the large single crystal for application. By using Zn to substitute Be and connecting the adjacent functional layers with B3O6 groups to synthesize a new NLO crystal, we have successfully synthesized a KBBF-like compound Cs3Zn6B9O21, which not only overcomes the strong layer habit of KBBF and the high toxicity of the beryllium oxide powders, but also exhibits the largest SHG effect in KBBF family, about 3.3 times of KDP. The characterization of Cs3Zn6B9O21 shows that the UV cut-off edge is about 200 nm and the calculated birefringence in visible region is about 0.06. 3. The effects of the rigid units on the structures and properties of borates Introducing the rigid unit AlO4 tetrahedron into borates, we have successfully designed and synthesized a new polar compound, NaBa4(AlB4O9)2Br3. And in order to better understand the effect of the rigid units on the symmetry of the framework, centrosymmetric NaBa4(B5O9)2F2Cl is also synthesized by using the B atoms to substitute the Al atoms. Comparing the structures and NLO properties SHG response of NaBa4(AlB4O9)2Br3 and NaBa4(B5O9)2F2Cl with those of Cs2B4SiO9 previously synthesized by our group, we have concluded that the stronger rigid degree of rigid units will lead to the more distortions of the B-O groups. Furthermore, the more distortions of the B-O groups will be more favorable for the SHG response of borates. 4. The syntheses and characterization of other new borates. During our research, we have also found several new borates with interesting crystal structures. They consist of the first two borate-carbonate mixed salts, Ba5(BO3)2(CO3)2 and Ba4Sr(BO3)2(CO3)2 synthesized with high temperature solid state method in the open system, five penta-borates with the same stoichiometric ratio yet not being isostructural, M3M'B5O10 (M= K, Rb; M'=Cd, Zn) and MBaB5O9(M= Na, K); several borates with the isolated [B12O24] groups, Li3KB4O8, LiNa2Sr8B12O24F6Cl, NaCaB2O4F and Na8Ca7MgB13O27F9; and an interesting Zn-containing borates with high B-O polymerization, Pb5Zn4B10O21. And in the last part of thesis, the crystal structures, optical and thermal properties of these compounds have been studied in detail.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3411
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Recommended Citation:
俞洪伟. 基于平面BO3、产业化晶体结构优化及刚性基元的倍频材料设计、合成及性能表征[D]. 北京. 中国科学院大学. 2014.
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