本文選題：深紫外光學(xué)晶體 + 非線性�。� 參考：《山西師范大學(xué)》2017年碩士論文

【摘要】：深紫外光學(xué)晶體材料的合成一直是許多科研人員關(guān)注的熱點(diǎn)。由于目前有商用價(jià)值的晶體比較少,而這一類型材料在醫(yī)學(xué)、軍事等領(lǐng)域又有著非常重要的應(yīng)用。因而在本課題的研究中,我們通過(guò)高溫固相反應(yīng),在磷酸鹽和硼鈹酸鹽這兩大體系中引入堿金屬和堿土金屬混合型陽(yáng)離子,合成了四例新化合物,并對(duì)它們的結(jié)構(gòu)和性能進(jìn)行了研究。結(jié)果如下:1、利用Cs-Mg-P-O反應(yīng)體系以及在此體系中引入d10組態(tài)的Zn~(~(2+)),先后合成了兩種新的磷酸鹽晶體,Cs_6Mg_6(PO_3)18(CMP)和Cs_2Mg Zn2(P_2O_7)_2(CMZP),并合成了它們的多晶粉末。CMP屬于單斜晶系,結(jié)晶于非中心對(duì)稱和極性P21空間群,晶胞參數(shù)為a=7.7437(4)?,b=34.1273(17)?,c=10.1063(5)?,β=90.414(2)?,V=2670.7(2)?3,Z=2。該化合物存在兩條獨(dú)立的一維[PO3]∞螺旋鏈,并與孤立的Mg O6八面體通過(guò)共享氧原子形成了一個(gè)新的三維陰離子骨架。非線性測(cè)試顯示CMP在紫外區(qū)的粉末倍頻效應(yīng)約為KH_2PO_4(KDP)的0.1倍,并且能實(shí)現(xiàn)第I類相位匹配,其弱的極性響應(yīng)被非線性系數(shù)的計(jì)算進(jìn)一步確認(rèn)。進(jìn)一步的偶極矩計(jì)算表明,弱的倍頻效應(yīng)主要來(lái)源于畸變的Cs On多面體。CMZP屬于單斜晶系,中心對(duì)稱P21/c空間群,晶胞參數(shù)為a=13.5270(14)?,b=7.4464(8)?,c=14.6905(15)?,β=90.746(4)?,V=1479.6(3)?3,Z=4。該化合物的結(jié)構(gòu)中含有一個(gè)新的[Mg Zn_2P_4O_20]14-結(jié)構(gòu)單元,這個(gè)結(jié)構(gòu)單元是由兩個(gè)孤立的P_2O_7二聚體,兩個(gè)無(wú)序的Mg/Zn O_4和一個(gè)Zn O_4四面體組成。這兩個(gè)化合物的紫外-可見(jiàn)漫反射測(cè)試表明紫外截止邊都低于190nm,能帶理論計(jì)算表明這主要?dú)w因于O和P原子以及Zn原子之間的電子躍遷。2、在Li_2O-B_2O_3-BeO這個(gè)體系中合成了Li_(13)Be7B_9O_(27)和Li_(13)Mg Be_6B_9O_(27)晶體,都結(jié)晶于六方晶系P63/m空間群,有相同的分子式Li_(13)ABe_6B_9O_(27)(A=Be,Mg)。Li_(13)Be_7B_9O_(27)的晶胞參數(shù)為a=7.72789(19)?,c=18.8399(6)?,V=974.38(4)?3,Z=2;Li_(13)Mg Be_6B_9O_(27)的晶胞參數(shù)為a=7.731?,c=18.888?,V=977.8?3,Z=2。這兩個(gè)化合物結(jié)構(gòu)中都含有新的[Be_6B_9O_(33)]∞雙層陰離子骨架,Li+和A~(2+)填充在陰離子骨架的空隙平衡電荷,不同的是它們的結(jié)構(gòu)屬于鏡面對(duì)稱的關(guān)系。需要特別指出的是,這兩個(gè)化合物含有罕見(jiàn)的AO_6三棱柱的配位環(huán)境(A=Be,Mg),尤其是前所未有的Be O_6三棱柱結(jié)構(gòu),擁有超長(zhǎng)的Be-O鍵長(zhǎng)(2.2373(7)?),這改變了傳統(tǒng)上Be-O基團(tuán)只有強(qiáng)的共價(jià)鍵而沒(méi)有完全離子鍵的認(rèn)識(shí)。光學(xué)測(cè)試顯示它們的紫外截止邊都低于190 nm,能帶理論計(jì)算解釋它們的光學(xué)性質(zhì)主要是由B-O和Be-O基團(tuán)之間的電子躍遷決定的。熱穩(wěn)定性分析說(shuō)明它們擁有優(yōu)良的熱穩(wěn)定性。這表明這兩種硼鈹酸鹽在深紫外都有潛在的應(yīng)用價(jià)值。
[Abstract]:The synthesis of deep ultraviolet optical crystal materials has always been a hot spot for many researchers. Because of the low commercial value of crystal, this kind of material has very important applications in the fields of medicine and military. Therefore, in this study, we use the high temperature solid state reaction, in phosphate and beryllium salt, two In the large system, four new compounds were synthesized by the introduction of alkali metal and alkaline earth metal mixed cations, and their structure and properties were studied. The results are as follows: 1, two new phosphate crystals, Cs_6Mg_6 (PO_3) 18 (CMP) and Cs_2M, were synthesized by the Cs-Mg-P-O reaction system and the Zn~ (~ (2+)) introduced into the system in this system. G Zn2 (P_2O_7) _2 (CMZP), and synthesized their polycrystalline powder.CMP belongs to the monoclinic system, crystallized in the non centrally symmetric and polar P21 space group, the cell parameters are a=7.7437 (4)? B=34.1273 (17)?, c=10.1063 (5)?, beta =90.414 (2)?, V=2670.7 (2)? 3. There are two independent one-dimensional spiral chains with two isolated eight sides. A new three-dimensional anion skeleton is formed through the shared oxygen atom. The nonlinear test shows that the powder doubling effect of CMP in the ultraviolet region is about 0.1 times that of KH_2PO_4 (KDP), and can achieve phase I phase matching. The weak polarity response is further recognized by the calculation of nonlinear coefficients. Further dipole moment calculation shows that the weak frequency doubling efficiency is shown. The distortion based Cs On polyhedron.CMZP belongs to the monoclinic system, the centrally symmetric P21/c space group, the cell parameters of a=13.5270 (14)?, b=7.4464 (8)?, c=14.6905 (15)?, beta =90.746 (4)?, V=1479.6 (3)? 3. The compound contains a new [Mg Zn_2P_4O_20]14- structural unit, and this structural unit is composed of two isolated instances. _7 two polymer, two disordered Mg/Zn O_4 and a Zn O_4 tetrahedron. The UV visible diffuse reflectance tests of the two compounds show that the ultraviolet cut-off edges are lower than 190nm, and the theoretical calculation shows that this is mainly attributed to the electron transition.2 between the O and P atoms and the Zn atoms, and the Li_ (13) is synthesized in the Li_2O-B_2O_3-BeO system. O_ (27) and Li_ (13) Mg Be_6B_9O_ (27) crystals are crystallized in the P63/m space group of six square crystal systems, with the same molecular Li_ (13) ABe_6B_9O_ (27) (A=Be, Mg).Li_ (13) Be_7B_9O_ (27) cell parameters for a=7.72789 (6)? 6? 974.38 (4)? 3 The compound structure contains a new [Be_6B_9O_ (33)] (33)] double layer anion skeleton, Li+ and A~ (2+) fill the gap equilibrium charge of the anion skeleton, and their structure is mirror symmetry. It is special to point out that these two compounds contain a rare AO_6 three prism coordination environment (A=Be, Mg), especially in the former. The unknown Be O_6 three prism structure has a long Be-O bond length (2.2373 (7)?), which changes the understanding that the traditional Be-O group has a strong covalent bond without a complete ionic bond. Optical tests show that their UV cut-off edges are lower than 190 nm, and theoretical calculations explain that their optical properties are mainly from the electricity between the B-O and Be-O groups. Zi Yueqian decided. The thermal stability analysis shows that they have excellent thermal stability. This indicates that these two kinds of borylate have potential application in deep ultraviolet.
【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】：2017
【分類號(hào)】：O734

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