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硼磷酸盐/磷酸盐光电功能晶体材料的研究
王颖
学位类型博士
导师潘世烈
2015-05-20
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料物理与化学
关键词硼磷酸盐 磷酸盐 光电功能材料 高温固相合成 晶体生长 光学性质
摘要

光电功能晶体材料,因其在激光和光电子学方面的广泛应用,而成为材料科学与工程领域研究的一个热点。本论文以探索新型的光电功能晶体材料为目标,基于国内外光电功能晶体材料的研究现状,提出了在无机硼磷酸盐、磷酸盐体系中设计和合成新材料的研究思路。通过常规的高温固相法,成功合成了20余种新化合物,并对这些化合物的性能进行了表征,主要取得的成果如下:1、五种碱金属硼磷酸盐:Li2Cs2B2P4O15,LiK2BP2O8,Li3K2BP4O14,Li3Rb2BP4O14和K7B2P5O19在M2O -B2O3-P2O5体系(M= 碱金属)中合成出了一系列碱金属硼磷酸盐。单晶结构分析表明前四种化合物的阴离子基团都是由结构基元相互连接形成二维层状结构,而最后一种则由孤立的[B2P5O19]阴离子团簇作为结构基元。这些化合物的结构基元和结构基元的组合方式在硼磷酸盐中是首次被发现。特别是Li2Cs2B2P4O15,Li3K2BP4O14,Li3Rb2BP4O14和K7B2P5O19的结构基元包含硼磷酸盐中反常的P-O-P连接方式,违背了晶体结构化学的鲍林第四原则。2、一种非中心对称的硼磷酸盐:RbPbBP2O8设计合成了硼磷酸盐化合物RbPbBP2O8,测定了其单晶结构,并采用泡生法生长了其大尺寸单晶,尺寸为23 mm × 18 mm × 7 mm。对该化合物的元素组分,晶体结构,热学性能,线性和非线性光学性质进行了表征。RbPbBP2O8的晶体结构中包含一种宝石类型的阴离子框架结构,该化合物为一致熔融化合物,其粉末倍频信号强度接近于KH2PO4,为非一类相位匹配化合物。该晶体物化性能稳定,不潮解,其透光范围可从380nm到6µm,热膨胀测试表现出各向同性的特性。3、两种金属硼酸-磷酸盐:Pb4O(BO3)(PO4)和Bi4O3(BO3)(PO4)通过对已知金属硼酸-磷酸盐的研究,设计合成了Pb4O(BO3)(PO4)和Bi4O3(BO3)(PO4);它们的晶体结构都是由以氧原子为中心的(OPb4)或(OBi4)四面体,以及孤立的BO3和PO4基团组成。对这两个化合物的热学和光学性质进行了表征。根据其结构特征和晶格马德隆能计算结果,我们首次提出一种基于BO3和PO4基团的相互替换的策略来设计和制备新的金属硼酸-磷酸盐。4、一系列钼磷酸盐化合物:RbMoO2PO4、Rb4Mo5P2O22和Cs4Mo5P2O22,以及固溶体CsxRb4-xMo5P2O22(x = 0~4)制备合成了一系列结构新颖的钼磷酸盐化合物,并对这些化合物的物化性质和结构性能关系进行了详细的研究。首次在多金属氧酸盐中发现了聚合的Strandberg型[Mo5P2O23]6-基元。此外,非中心对称的Rb4Mo5P2O22和Cs4Mo5P2O22,由于晶体中结构基元的定向排列,能够产生中等强度的倍频效应。5、其他金属磷酸盐的研究在上述的研究过程中得到了数十种硼磷酸盐/磷酸盐化合物,对它们的结构进行了单晶衍射测试。这些化合物中,K6Na3Al3P6O24具有铝磷酸盐中独特的三维[Al3P6O24]9-阴离子基团框架结构;Cs6Y2(PO4)4和Cs6Gd2(PO4)4可作为荧光基质材料。

其他摘要

Optoelectronic functional materials are of current interest due to their applications in laser and optoelectronic devices. In this dissertation, the research goal focuses on discovering new optoelectronic functional materials. The current optoelectronic functional materials were reviewed in the light of their structure and related properties. We put forward a research approach on designing and synthesizing new optoelectronic functional materials based on borophosphates and phosphates. By using conversional high temperature solid-state reaction, we have obtained more than 20 new compounds, and have performed general characterizations on their physical and chemical properties. The main achievements are concluded in the following: 1. Five alkali metal borophosphates: Li2Cs2B2P4O15, LiK2BP2O8, Li3K2BP4O14, Li3Rb2BP4O14, and K7B2P5O19 In the M2O - B2O3 - P2O5 (M = alkali metal) system, we have obtained a series of alkali metal borophosphates. The single crystal X-ray crystallographic analysis indicates that the anionic partial structures of the first four compounds are two dimensional layers composed by fundament building units, while the last compound in this series contains an isolated [B2P5O19] anionic partial structure. The fundament building units as well as their linkage modes are observed for the first time in borophosphates. In particular, three fundament building units: [B4P8O30], [B(P2O7)2], and [B2P5O19] found in these compounds contain an abnormal P-O-P linkage, which is extremely rare and gives another example of the violation of Pauling’s fourth rule in borophosphates. 2. A new noncentrosymmetric borophosphate: RbPbBP2O8 A new noncentrosymmetric borophosphate, RbPbBP2O8, has been synthesized and its high quality single crystal with dimensions up to 23 mm × 18 mm × 7 mm was successfully grown by the Kyropoulos method for the first time. Elemental analysis, thermal analysis and measurements on the linear and nonlinear optical properties were performed on the reported crystal. The structure analysis reveals that it features a diamond-like framework composed of BO4 and PO4 tetrahedra interconnected by MO8 (M = Rb/Pb) distorted polyhedra. The powder second harmonic generation response of RbPbBP2O8 is similar to that of KH2PO4 and it is a type I nonphase-matchable material. The crystal is found to be chemical stable, nondeliquescent, and its transparent area ranges from 380 nm to 6 μm. It also exhibits almost an isotropic property in thermal expansion. 3. Two metal borate-phosphates: Pb4O(BO3)(PO4) and Bi4O3(BO3)(PO4) After carefully analyzing the known borate–phosphates, we have designed and synthesized Pb4O(BO3)(PO4) and Bi4O3(BO3)(PO4). The structures of the two compounds were determined by single-crystal X-ray diffraction. The two compounds have similar crystal structures consisting of oxygen-centered (OPb4) or (OBi4) tetrahedra as well as isolated BO3 and PO4 groups. Thermal analyses, IR spectroscopy and UV-vis-NIR diffuse reflectance spectroscopy have also been performed on the reported compounds. Structural comparison and the Madelung energy calculation indicate that the title compounds also exhibit a strong correlation with the known metal borates and phosphates. In addition, a strategy of BO3–PO4 substitution is proposed for designing new borate–phosphates. 4. A series of molybdenum phosphates:RbMoO2PO4, Rb4Mo5P2O22, and Cs4Mo5P2O22, as well as the solid solution compounds CsxRb4-xMo5P2O22 (x = 0~4) A series of molybdenum phosphates have been synthesized by standard solid-state reactions, and their crystal structures and physical properties were characterized. We have found the first example of Strandberg-type polyoxometalate with one-dimensional straight chains composed by polymerized [Mo5P2O23]6? units. Rb4Mo5P2O22 and Cs4Mo5P2O22 not only show novel structures, but also show moderate SHG responses, originating from the favorable orientations of fundamental building units. 5. Other metal phosphates During the

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4237
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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王颖. 硼磷酸盐/磷酸盐光电功能晶体材料的研究[D]. 北京. 中国科学院大学,2015.
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