新型锑碘酸盐的合成、结构和光学性质的研究

发布时间：2018-09-01 07:29

【摘要】：在锑碘酸盐晶体中,五价碘(I5+)因有一对未成键电子对,可以形成不对称的碘氧基团,易使生成的化合物结构具有多样性,故而在半导体、非线性等方面有良好的应用前景,是目前研究的热点。而锑(Sb)通常显示+3价和+5价两种价态,和氧结合可以形成SbO_3,Sb O_6等多种基团,因而在结构方面具有很好的灵活性和多样性,而且锑酸盐是一种半导体材料,在非线性、光催化等领域有广泛的报道。在本课题的研究中,我们通过水热合成方法,在碘酸盐中引入可以在结构上起灵活作用的Sb,得到了新颖的锑碘酸盐、锑酸盐晶体等材料,并对其结构和性质进行了研究。研究内容主要分为五章:第一章是前言部分,主要对半导体激光材料以及碘酸盐、锑酸盐晶体材料的研究背景进行了介绍,具体介绍碘酸盐、锑酸盐在结构方面的特点。同时还阐述了本课题的选题意义和研究进展。第二章用水热法合成两个锑碘类化合物,分别是锑碘酸钾(KSbI_6O_(18))和锑碘化胺((NH_4)_2(H_3O)Sb_2I_9),两者均为六方晶系。其中锑碘酸钾KSbI_6O_(18)空间群为R-3。晶胞参数为a=11.3057(6)?,c=11.3340(8)?,γ=120°,z=3。这个化合物是一个三维的网状结构,其中包含一个新的具有S6对称性的零维的螺旋I_6O_(18)环,这个环与SbO_6八面体共氧连接,形成独特的[Sb(I_6O_(18))]-阴离子腔,K+填充在[Sb(I_6O_(18))]-阴离子腔中,起到平衡电荷的作用。通过对KSb I_6O_(18)的光学性质研究发现,它在半导体领域具有潜在的应用前景。锑碘化胺(NH_4)_2(H_3O)Sb_2I_9的空间群P6-2c,晶胞参数a=9.8686(4)?,c=23.2605(10)?,α=90°,γ=120°,z=2。此化合物中Sb与I直接相连形成经典的[Sb_2I_9]~(3-)阴离子基团。通过对它的光学性质分析,发现锑碘化胺同样有潜在的半导体特征。第三章用Sb_2O_3、BaF_2等合成新的锑酸盐,锑氟酸Sb_3O_4F。化合物的晶胞参数为a=5.6376(2)?,b=4.7151(1)?,c=20.3660(7)?,α=90°,β=94.354(3)°,γ=90°,z=4,属于单斜晶系,空间群为P21/c。其中Sb_3O_4F为层状结构,这个层状结构是由[Sb_2O_4]~(2-)和[SbF]~(2+)基团构成的,相邻的[Sb_2O_4]~(2-)阴离子基团共氧形成了沿c轴的一维的[Sb_4O_8]_4-链,这个一维链与两个[Sb F]~(2+)基团桥链形成二维的层状结构。另外,通过固体紫外的测试,发现化合物的带隙值较大为3.58eV,初步判定为宽带隙半导体。第四章介绍了一个新的碘酸镁晶体β-MgI_2O_6,化合物的晶胞参数为a=5.4968(4)?,b=5.1170(10)?,c=9.4489(7)?,β=90.314(7)°,z=2,属于单斜晶系,空间群为P21,单位晶胞中包括一个镁原子和两个碘原子,Mg是六配位,形成扭曲的MgO_6八面体,与扭曲的IO_3基团共氧连接。整个化合物有沿着-b轴方向的宏观极性,属于非中心对称的化合物。第五章对本论文的相关工作进行总结。
[Abstract]:In antimony iodide crystals, pentavalent iodine (I5) can form asymmetric iodide groups because of a pair of unbonded electrons, which makes the resulting compounds have a wide variety of structures, so they have a good application prospect in semiconductor, nonlinear and so on. Is the current research hot spot. However, antimony (Sb) usually shows three valence and five valence states, and can combine with oxygen to form a variety of groups, such as SbO_3,Sb O _ 6, so it has good flexibility and diversity in structure, and antimony is a semiconductor material, which is nonlinear. Photocatalysis and other fields have been widely reported. In the research of this subject, we have obtained novel antimony iodate, antimonate crystal and other materials by hydrothermal synthesis method, and we have studied its structure and properties by introducing Sb, which can play a flexible role in structure. The main research contents are divided into five chapters: the first chapter is the preface. The research background of semiconductor laser materials, iodate and antimonate crystal materials are introduced, and the structure characteristics of iodate and antimonate are introduced in detail. At the same time, the significance and research progress of this topic are expounded. In chapter 2, two antimony and iodine compounds, potassium antimony iodide (KSbI_6O_ _ (18) and antimony iodide (NH_4) _ 2 (H _ 3O) Sb_2I_9, are synthesized by hydrothermal method, both of which are hexagonal. The space group of KSbI_6O_ _ (18) is R-3. The unit cell parameters are 11.3057 (6), 11.3340 (8), and 120 掳, respectively. The compound is a three-dimensional reticular structure containing a new S6-symmetric, zero-dimensional helical I _ 6O _ (18) ring that connects with SbO_6 octahedron to form a unique [Sb (I _ 6O _ (18)] -anion cavity filled with [Sb (I _ S _ 6O _ (18)] -anion cavity. Play the role of balancing the charge. By studying the optical properties of KSb I _ 6O _ (18), it is found that it has a potential application prospect in semiconductor field. The space group P6-2cof stibium iodide amine (NH_4) 2 (H3O) Sb_2I_9 is P6-2c. the unit cell parameter (a) 9.8686 (4) is 23.2605 (10) (10). In this compound, Sb is directly linked to I to form a classical [Sb_2I_9] ~ (3-) anionic group. By analyzing its optical properties, it is found that antimony iodide also has potential semiconductor characteristics. Chapter 3: synthesis of new antimonates, antimony fluoride Sb_3O_4F. by Sb_2O_3,BaF_2 et al. The unit cell parameters of the compound are a ~ (5.6376) (2) ~ 4.7151 (1) ~ (2) ~ (1) ~ (1) C ~ (+) ~ (20) 3660 (7), 伪 ~ (90) 掳, 尾 ~ (94) 354 (3) 掳, 纬 ~ (90) ~ (90) 掳~ (zN) ~ (4), which belong to monoclinic system, and the space group is P21 ~ (c) ~ (-1). Sb_3O_4F is a layered structure, which is composed of [Sb_2O_4] ~ (2-) and [SbF] ~ (2) groups. The adjacent [Sb_2O_4] ~ (2-) anionic group co-oxygen forms a one-dimensional [Sb_4O_8] 4-chain along the c-axis, which forms a two-dimensional layered structure with two [Sb F] ~ (2) bridged chains. In addition, it was found that the band gap value of the compound was 3.58 EV, which was determined to be a wide band gap semiconductor. In chapter 4, a new magnesium iodate crystal 尾 -MgI _ 2O _ 6 is introduced. The unit cell parameter of the compound is a ~ (5.4968) (4) ~ 5.1170 (10) C ~ (9.4489) (7), 尾 _ (90.314) (7) ~ (?) ~ (2), which belongs to monoclinic system. The space group is P21.The unit cell consists of a magnesium atom and two iodine atoms, which are hexagonal and form a twisted MgO_6 octahedral body. The oxygen is connected to the twisted IO_3 group. The whole compound has macro polarity along the-b axis and belongs to a non-centrosymmetric compound. The fifth chapter summarizes the related work of this paper.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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