【作者】 周树才；

【导师】 孙海清；

【作者基本信息】 山东科技大学 ， 材料工程， 2011， 硕士

【摘要】 自从发现非线性光学现象以来,人们在新的非线性光学材料探索方面做了大量工作。金属有机配合物晶体材料结合了有机材料和无机材料的优点,通过改变金属有机配合物中心金属离子或配体,可以有效地调控、优化配合物的物理化学性质,在非线性光学领域吸引了众多研究者的目光。在所报道的金属有机配合物中,中心金属一般都选择IIB族金属,其中以烯丙基硫脲(简称AT)为配体的ATM’X型晶体具有较强的非线性光学效应,稳定的物化性质,可获得优质晶体,是一类性能优良的非线性光学材料。这类配合物的通式是ATM’X,其中M’=Cd、Hg, X=Cl、Br、Ⅰ等。本文在参阅大量国内外文献的基础上介绍了非线性光学基本原理、非线性光学晶体材料的分类及应用,简述了金属有机配合物非线性光学晶体材料的发展情况。具体研究内容如下：1、首次设计、合成、生长出了ATCI配合物新晶体。该晶体生长的最佳pH值在3-4之间,降温速率为0.1℃\天；选择的溶剂是蒸馏水和乙醇。2、通过对ATCI晶体的元素分析确定了晶体的分子组成；进行了X射线衍射物相鉴定确定了ATCI晶体属于三方晶系,空间群是R3c；对晶体进行了光谱学、热学和非线性光学等性质的研究,结果表明配合物中S与Cd配位；二阶非线性光学效应测试显示ATCI晶体的效应与尿素相当。3、对ATCC、ATCB、ATMC和ATCI这四种晶体进行了红外光谱、热学和粉末倍频效应等性质的比较研究,探讨了性质结构之间的内在规律性。结果表明,ATCI晶体与ATCC、ATCB、ATMC具有相似的性质,随着中心金属原子序数的增加,配合物材料的热稳定性提高,非线性光学效应变大。本文研究对ATM’X型非线性光学晶体的生长、性能表征及应用有一定的指导意义,在探索新型配合物非线性光学材料方面具有重要的价值。更多还原

【Abstract】 A lot of researches have been done since the first observation of nonlinear optical phenomenon. Organometallic complex materials have been attracting many researchers in the nonlinear optical field, because of its coordination compounds the merits of both inorganic and organic materials that the physical and chemical properties of the complex can be effectively dominated by changing the central ions and ligand. As reported in the organometallic materials, mostly have group IIB metals as center ions, Among them, metal-allylthiourea coordination compounds ATM’X type is prominent. ATM’X type crystal has strong NLO efficiency, deep UV cut-off wavelength and stable physicochemical properties as well as the crystal growth can be realized.The general formula of these coordination compound is ATM’X [where AT=(allylthiourea)=C4H8N2S, M’=Cd or Hg, X=Cl, Br orⅠ].In this paper, the basic theory of nonlinear optics, the classification of nonlinear optical crystal materials and the application of nonlinear optical crystal materials were introduced and the development of organometallic complex optical materials, are reviewed on the basis of studying lots of literature at home and abroad. The summaries of compounds of this thesis are as follows:1. The coordination crystal tri-allylthiourea cadmium iodide was synthesized and grown for the first time. The crystal growth optimal pH value is 3～4, Cooling rate is 0.1℃\day; Solvent is distilled water and ethanol.2. The the element analysis of ATCI crystal, determine the molecular structure of this crystals. Through the powder X-ray content phase identification and Rietveld refinement determined the wafer ATCI crystal belong to trigonal system, belong to space group R3c; The spectroscopy, calorifics and NLO properties of the ATCI crystal. Some of the conclusions are: Complexes with Cd slots in S, ATCI shows powder SHG efficiency comparative to urea.3. The structures and properties of the ATCC, ATCB, ATMC and ATCI crystal were systematically studied. Results show that ATCI crystals and ATCC, ATCB and ATMC are Similar properties. Along with the increase of central metal atom number, complexes material thermal stability improved, nonlinear optical effect greatens.This paper will do help in study of the series of ATM’X type, both in their crystal growth, properties characterization and appliance. These studies are important for searching at novel coordination compound NLO materials.更多还原