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磷酸盐和硼酸盐紫外光学晶体的合成及性能研究
买尔哈巴·阿不都热合曼
Subtype博士
Thesis Advisor潘世烈
2018-05-24
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料物理与化学
Keyword非线性光学晶体 硼酸盐 磷酸盐 光学性质
Abstract

探索紫外/深紫外光学晶体是当前研究的热点之一。本文以磷酸盐、硼酸盐作为研究体系,在体系中通过替换金属阳离子,增大硼、磷/金属阳离子的比例等策略,采用高温熔液法获得了近20种新化合物。经合成并对晶体结构进行解析发现其中有9种化合物结晶在非中心对称(NCS)空间群,进一步对得到的化合物的性能进行了表征。1. 具有短紫外截止边的非线性光学晶体MIMII2(PO3)5 (MI = K, Rb和Cs, MII = Pb, Ba)及性能表征在MI-MII-P-O (MI = K, Rb和Cs, MII = Pb, Ba)体系中获得了6种非线性光学(NLO)晶体,KBa2(PO3)5, RbBa2(PO3)5, CsBa2(PO3)5, KPb2(PO3)5, RbPb2(PO3)5, CsPb2(PO3)5,均结晶于Pn (No. 7)空间群。其结构描述为:一维(1D)[PO3]∞链和MIIOn多面体链接形成三维(3D)网络,碱金属MI (K, Rb和Cs)填充在间隙内。经光学性质的研究发现,KPb2(PO3)5, KBa2(PO3)5和RbBa2(PO3)5倍频效应的大小约为0.5倍KDP,RbPb2(PO3)5化合物的效应为0.3倍KDP,并且都能够实现相位匹配。在含Pb的体系中探索深紫外非线性光学(NLO)晶体是个挑战,因为Pb原子的存在会使化合物的截止边红移。有趣的是,KPb2(PO3)5晶体的深紫外透过光谱实验表明,该化合物的紫外截止边是177nm,这是含铅的NLO晶体中紫外截止边最短的化合物;KBa2(PO3)5晶体的透过光谱结果显示,其紫外截止边到176nm;此结果表明KPb2(PO3)5和KBa2(PO3)5在深紫外区域有潜在的应用价值。另外,基于密度泛函理论,从电子结构的角度阐明了KPb2(PO3)5化合物紫外截止边蓝移的原因,即Pb原子弱的立体活性使其紫外截止边蓝移。双折射测试结果显示KPb2(PO3)5的双折射值为0.030@589.3nm。偶极矩计算的结果表明,KPb2(PO3)5, KBa2(PO3)5, RbBa2(PO3)5和RbPb2(PO3)5的倍频效应的来源是,结构中的KO7/RbOn/CsO8, PbOn/BaO8多面体和PO4四面体畸变的协同效应,这也解释了该系列化合物结构与光学性质之间的关系。2. 阳离子替换在MIMIIP3O9中 (MI:碱金属 MII:碱土金属,d10过渡金属,含有孤电子对的金属)的应用在具有P3O9环状结构的MIMIIP3O9中,通过替换MI和MII金属阳离子得到了5种新化合物,其中RbCdP3O9, KMgP3O9和CsPbP3O9三者结晶在非中心对称(NCS)空间群P6(_)c2和Pna21。粉末倍频效应测试表明,KMgP3O9的粉末倍频强度为0.2 × KDP,RbCdP3O9和CsPbP3O9的效应为0.1倍KDP。UV-Vis-NIR 漫反射光谱测试表明RbCdP3O9和CsSrP3O9的紫外截止边在190nm,CsPbP3O9的在220nm,KMgP3O9, RbMgP3O9和RbCaP3O9三者的在230nm。通过第一性原理计算了化合物的能带大小和态密度。这系列化合物的成功合成表明,替换化合价、离子半径及配位环境相似的金属阳离子是探索新化合物的有效方法之一。3. 复合碱金属硼酸盐中具有穿插结构的化合物Na2M2B20O32 (M = Rb, Cs)和含有新的结构基元B40O77的化合物Li4Cs4B40O64在结构多样化的硼酸盐体系中,硼和金属阳离子(B/M)的比例会影响结构中B-O基团的聚合度及结构框架。通过增大B/M比例,在复合碱金属硼酸盐体系中获得了3种化合物,Na2M2B20O32 (M = Rb, Cs)和Li4Cs4B40O64。经单晶数据解析发现Na2M2B20O32 (M = Rb, Cs)结晶在C2/c空间群,而Li4Cs4B40O64属于P1(_)空间群。据我们所知,在不含水的复合碱金属体系中Na2M2B20O32 (M = Rb, Cs)是首例含有两种穿插结构的化合物,Li4Cs4B40O64结构中包含该体系中最大的B-O结构基元B40O77。从拓扑学的角度对比了碱金属和复合碱金属硼酸盐体系中含有穿插结构的化合物的结构,讨论了该体系中B/M比例和B-O结构基元之间的规律,并详细的讨论了上述3个化合物结构中的差别及不同金属阳离子对结构的影响。此外对Na2Rb2B20O32和Na2Cs2B20O32两个化合物进行了光谱学性质的测试及理论计算。4. 含有不同类型P-O链和环状结构的磷酸盐: A3Sr2P7O21 (A = Rb, Cs)通过传统的高温固相法,获得了结构中包含两种孤立的P-O基元的化合物Rb3Sr2P7O21和Cs3Sr2P7O21;这两个化合物虽然具有相同的化学计量比却结晶在不同的空间群。据我们所知,Rb3Sr2P7O21是首例含有两种孤立1D [PO3]∞链的结构,然而Cs3Sr2P7O21结构中P-O基团包括1D [PO3]∞链和P4O12环,这种结构在磷酸盐中也是比较少见的。经过结构对比,讨论了A位阳离子对结构的影响,统计了含有两种P-O基元的化合物并讨论了磷与金属阳离子(P/M)比例和P-O基团在结构中的存在方式。UV-Vis-NIR 漫反射光谱测试表明两个化合物的紫外截止边在260nm;理论计算结果显示Rb3Sr2P7O21是直接带隙化合物,能带大小为4.97eV;导带和价带的组成成分表明PO4和Rb决定了该化合物的能带。5. 其他磷酸盐的研究结构中BO3和PO4阴离子基团的替换也是获得新化合物的有效途径之一。用此方法我们获得了3种含铅的磷灰石结构的化合物MPb4(PO4)3 (M = K, Rb和Cs),并且对其光学性质进行了研究。UV-Vis-NIR 漫反射光谱测试表明三个化合物的紫外截止边在300nm。热力学分析表明KPb4(PO4)3, RbPb4(PO4)3为同成分熔融化合物,而CsPb4(PO4)3为非同成分熔融化合物。理论计算表明RbPb4(PO4)3的能带的计算值为3.28eV,计算的双折射的值为0.014。红外光谱测试进一步验证了PO4四面体的存在。

Other Abstract

Finding new UV/deep-UV optical materials is one of the current interests. In this dissertation, several e?ective strategies are used based on phosphates and borates: increasing the ratio of borate, phosphate/metals (B, P / M); mutually substituting the metal cations in the host crystal structure. By using a high-temperature solution method, near 20 new compounds have been successfully synthesized, among them 9 compounds are belonging to non-centrosymmetric space group. The general characterizations have been performed.1. Nonlinear optical polyphosphates MIMII2(PO3)5 (MI = K, Rb and Cs, MII = Pb, Ba) with short cuto? edges and properties In the MI-MII-P-O (MI = K, Rb and Cs, MII = Pb, Ba) system, 6 nonlinear optical(NLO) phosphates KBa2(PO3)5, RbBa2(PO3)5, CsBa2(PO3)5, KPb2(PO3)5, RbPb2(PO3)5 and CsPb2(PO3)5 successfully obtained. All of them crystallize in the space group of Pn (No. 7) and have been 1D [PO3]∞ and MIIOn polyhedra construct the 3D networks with the K/Rb/Cs atoms residing in the space. NLO property test results imply that KPb2(PO3)5, KBa2(PO3)5 and RbBa2(PO3)5 display moderate powder second harmonic generation (SHG) intensities (0.5 × KDP), and RbPb2(PO3)5 shows 0.3 × KDP. All of them are phase matchable. Interestingly, KPb2(PO3)5 exhibits a short UV cut-o? edge of 177 nm, which is the shortest UV cut-o? edge among Pb-containing NLO crystals. KBa2(PO3)5 also has a short UV cut-o? edge of 176 nm, demonstrating that both of them are promising deep UV NLO materials. The theoretical calculations based on density functional theory were performed to better understand the blue-shift of the band gap in KPb2(PO3)5. Based on the stereoactive lone pair analysis, weak stereochemistry contribution of lead atom resulted in the lower cut off edge in KPb2(PO3)5. Furthermore, the birefringence measurement shows that the birefringence of KPb2(PO3)5 is about 0.030 at 589.3 nm. By calculating dipole moments of KO7/RbOn/CsO8, PbOn/BaO8 polyhedra and PO4 tetrahedra in the structures of KPb2(PO3)5, KBa2(PO3)5, RbBa2(PO3)5 and RbPb2(PO3)5, the relationship between structures and NLO properties also have been discussed.2. MIMIIP3O9 (MI = Rb, MII = Cd, Mg, Ca; MI = Cs, MII = Pb, Sr; MI = K, MII =Mg): Cation substitution application in cyclophosphate family By substituting the MI and MII metal cations in the cyclophosphate family, 5 new phosphates have been synthesized. Among them, RbCdP3O9, CsPbP3O9 crystallize in NCS space groups P6(_)c2, Pna21, and CsSrP3O9, RbMgP3O9 and RbCaP3O9 belong to Pnma. As a one of the cyclophosphate members, KMgP3O9 exhibits a SHG intensity of about 0.2 times that of KDP, RbCdP3O9 and CsPbP3O9 also show SHG response of 0.1 × KDP. UV-Vis-NIR di?use re?ectance results indicate that the cut-o? edges are below 190 nm (for RbCdP3O9 and CsSrP3O9), 220 nm (for CsPbP3O9), and 230 nm (for KMgP3O9, RbMgP3O9 and RbCaP3O9). Furthermore, theoretical calculations based on density functional theory and dipole moments are calculated to investigate the relationship between structural and NLO properties. Those results indicated that cation substitution is one of the e?ective strategies to get new compounds.3. Three mixed-alkaline borates: Na2M2B20O32 (M = Rb, Cs) with two interpenetrating three-dimensional B?O networks and Li4Cs4B40O64 with fundamental building block B40O77 Borates possess very rich structural chemistry, and the ratio of borate/metals (B/M) has an influence on polymerization and B-O network formations. With the increasing the ratio of B/M, three mixed-alkaline borates Na2M2B20O32 (M = Rb, Cs) and Li4Cs4B40O64 are obtained. Single-crystal X-ray determination shows that Na2M2B20O32 (M = Rb, Cs) crystallize in C2/c space group, and Li4Cs4B40O64 belongs to P1(_). To the best of our knowledge, Na2M2B20O32 (M = Rb, Cs) are the ?rst samples that the two interpenetrating 3D B-O nets coexist in one anhydrous mixed-alkali metal borate structure. Li4Cs4B40O64 displays high B-O polymerization with a new fundamental building block B40O77. The detailed structure comparisons among compounds with interpenetrating 3D frameworks are discussed from topologically point, also e?ect of cation on the framework also has been discussed. UV-Vis-NIR di?use re?ectance spectra, IR spectra, and theoretical calculations were performed for compounds Na2Rb2B20O32 and Na2Cs2B20O32. 4. A3Sr2P7O21 (A = Rb, Cs): Two polyphosphates based on di?erent types of P-O chains and ring structures Through a spontaneous nucleation method, two polyphosphates, Rb3Sr2P7O21 and Cs3Sr2P7O21, with two types of polymerization of PO4 groups were obtained. Although the two stoichiometrically equivalent metal phosphates consist of similar structural feature groups, they crystallize in different space groups. To the best of our knowledge, Rb3Sr2P7O21 is the ?rst example of two kinds of [PO3]∞ linear chains coexisting in one phosphate structure. While, in the structure of Cs3Sr2P7O21, the isolated P4O12 rings and the 1D [PO3]∞ chains can be observed, which is also rare in phosphates. The effect of cations on the polymerization of the PO4 groups, structure comparison among phosphates including two types of PO4 groups, and the relationship between PO4 groups and the ratio of P/M are discussed. The UV-Vis-NIR di?use re?ectance spectra results show that cuto? edge of both compounds are below 260 nm. Theoretical calculation suggests that Rb3Sr2P7O21 has a direct band gap of 4.97 eV.5. Other metal phosphates and their properties In crystal engineering, modi?cation of the crystal structure by substitution of BO3 and PO4 is one of the ef?cient methods to obtain new structures. By employing these strategies, three apatite-type phosphate compounds KPb4(PO4)3, RbPb4(PO4)3 and CsPb4(PO4)3 have been synthesized by high-temperature solid state method. The UV-Vis-NIR diffuse re?ectance spectra indicate that they present no obvious absorption peaks from 300 to 2500 nm. Thermal behavior analysis implied that KPb4(PO4)3, RbPb4(PO4)3 melts congruently, while CsPb4(PO4)3 exhibits incongruent melting habit. Theoretical calculation result reveals that RbPb4(PO4)3 has an indirect gap of 3.28 eV. The IR spectra con?rm the existence of the PO4 groups.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/5441
Collection材料物理与化学研究室
Recommended Citation
GB/T 7714
买尔哈巴·阿不都热合曼. 磷酸盐和硼酸盐紫外光学晶体的合成及性能研究[D]. 北京. 中国科学院大学,2018.
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