【摘要】：在銻碘酸鹽晶體中,五價(jià)碘(I5+)因有一對(duì)未成鍵電子對(duì),可以形成不對(duì)稱的碘氧基團(tuán),易使生成的化合物結(jié)構(gòu)具有多樣性,故而在半導(dǎo)體、非線性等方面有良好的應(yīng)用前景,是目前研究的熱點(diǎn)。而銻(Sb)通常顯示+3價(jià)和+5價(jià)兩種價(jià)態(tài),和氧結(jié)合可以形成SbO_3,Sb O_6等多種基團(tuán),因而在結(jié)構(gòu)方面具有很好的靈活性和多樣性,而且銻酸鹽是一種半導(dǎo)體材料,在非線性、光催化等領(lǐng)域有廣泛的報(bào)道。在本課題的研究中,我們通過水熱合成方法,在碘酸鹽中引入可以在結(jié)構(gòu)上起靈活作用的Sb,得到了新穎的銻碘酸鹽、銻酸鹽晶體等材料,并對(duì)其結(jié)構(gòu)和性質(zhì)進(jìn)行了研究。研究?jī)?nèi)容主要分為五章:第一章是前言部分,主要對(duì)半導(dǎo)體激光材料以及碘酸鹽、銻酸鹽晶體材料的研究背景進(jìn)行了介紹,具體介紹碘酸鹽、銻酸鹽在結(jié)構(gòu)方面的特點(diǎn)。同時(shí)還闡述了本課題的選題意義和研究進(jìn)展。第二章用水熱法合成兩個(gè)銻碘類化合物,分別是銻碘酸鉀(KSbI_6O_(18))和銻碘化胺((NH_4)_2(H_3O)Sb_2I_9),兩者均為六方晶系。其中銻碘酸鉀KSbI_6O_(18)空間群為R-3。晶胞參數(shù)為a=11.3057(6)?,c=11.3340(8)?,γ=120°,z=3。這個(gè)化合物是一個(gè)三維的網(wǎng)狀結(jié)構(gòu),其中包含一個(gè)新的具有S6對(duì)稱性的零維的螺旋I_6O_(18)環(huán),這個(gè)環(huán)與SbO_6八面體共氧連接,形成獨(dú)特的[Sb(I_6O_(18))]-陰離子腔,K+填充在[Sb(I_6O_(18))]-陰離子腔中,起到平衡電荷的作用。通過對(duì)KSb I_6O_(18)的光學(xué)性質(zhì)研究發(fā)現(xiàn),它在半導(dǎo)體領(lǐng)域具有潛在的應(yīng)用前景。銻碘化胺(NH_4)_2(H_3O)Sb_2I_9的空間群P6-2c,晶胞參數(shù)a=9.8686(4)?,c=23.2605(10)?,α=90°,γ=120°,z=2。此化合物中Sb與I直接相連形成經(jīng)典的[Sb_2I_9]~(3-)陰離子基團(tuán)。通過對(duì)它的光學(xué)性質(zhì)分析,發(fā)現(xiàn)銻碘化胺同樣有潛在的半導(dǎo)體特征。第三章用Sb_2O_3、BaF_2等合成新的銻酸鹽,銻氟酸Sb_3O_4F�；衔锏木О麉�(shù)為a=5.6376(2)?,b=4.7151(1)?,c=20.3660(7)?,α=90°,β=94.354(3)°,γ=90°,z=4,屬于單斜晶系,空間群為P21/c。其中Sb_3O_4F為層狀結(jié)構(gòu),這個(gè)層狀結(jié)構(gòu)是由[Sb_2O_4]~(2-)和[SbF]~(2+)基團(tuán)構(gòu)成的,相鄰的[Sb_2O_4]~(2-)陰離子基團(tuán)共氧形成了沿c軸的一維的[Sb_4O_8]_4-鏈,這個(gè)一維鏈與兩個(gè)[Sb F]~(2+)基團(tuán)橋鏈形成二維的層狀結(jié)構(gòu)。另外,通過固體紫外的測(cè)試,發(fā)現(xiàn)化合物的帶隙值較大為3.58eV,初步判定為寬帶隙半導(dǎo)體。第四章介紹了一個(gè)新的碘酸鎂晶體β-MgI_2O_6,化合物的晶胞參數(shù)為a=5.4968(4)?,b=5.1170(10)?,c=9.4489(7)?,β=90.314(7)°,z=2,屬于單斜晶系,空間群為P21,單位晶胞中包括一個(gè)鎂原子和兩個(gè)碘原子,Mg是六配位,形成扭曲的MgO_6八面體,與扭曲的IO_3基團(tuán)共氧連接。整個(gè)化合物有沿著-b軸方向的宏觀極性,屬于非中心對(duì)稱的化合物。第五章對(duì)本論文的相關(guān)工作進(jìn)行總結(jié)。
[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 擄, 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), 偽 ~ (90) 擄, 尾 ~ (94) 354 (3) 擄, 緯 ~ (90) ~ (90) 擄~ (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.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O641.4

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