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碱金属氟硼酸盐深紫外光学晶体的合成与性质研究
史国强
学位类型硕士
导师张方方
2017-05-31
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料工程
关键词光学晶体 氟硼酸盐 深紫外 双折射 非线性光学
摘要

深紫外光学晶体在光通信和激光系统等领域有重要的应用。例如,应用于光隔离器、光学起偏器、193 nm光刻偏振仪、紫外光分光光度计、深紫外拉曼光谱和荧光光谱仪的深紫外双折射晶体,以及被应用于半导体加工行业、超高分辨率光电子能谱和激光光刻领域的深紫外非线性光学晶体等。因此,深紫外光学晶体成为材料研究领域的一个热点。本论文致力于设计并合成可应用于深紫外波段的光学晶体。考虑到光学晶体在深紫外区域的透过问题,我们向硼酸盐结构中引入电负性最大的氟离子,同时选用不含d?d或f?f电子跃迁的碱金属离子作为阳离子,制备有利于深紫外光透过的碱金属氟硼酸盐。碱金属氟硼酸盐具有相对较短的紫外截止边,同时晶体结构中一致排列的极性[BOF]基团可产生较大的光学各向异性,有利于获得较大的双折射率。本文提出了碱金属氟硼酸盐的合成策略,采用固相法成功合成了三种碱金属氟硼酸盐,并且对这三种晶体进行了性质表征及理论分析,主要内容如下:1. 采用高温固相法合成了Na2B6O9F2 和Na3B7O11F2化合物,并通过自发结晶的方法生长了小尺寸单晶。Na2B6O9F2结晶于单斜晶系,空间群为P21/c,晶胞参数为a = 8.1964(12) ?,b = 13.0005(19) ?,c = 7.8955(11) ?,β = 90.750(2) °,Z = 4,V = 841.3(2) ?3。在Na2B6O9F2的晶体结构中,阴离子骨架为二维的[B6O9F2]2?层。漫反射光谱和透过光谱表明Na2B6O9F2在紫外-可见-近红外光谱区无明显吸收,紫外截止边为169 nm。采用油浸法,对晶体的折射率进行了测试,结果表明其在589.3 nm处的双折射率不小于0.08。该晶体物化性能稳定,可采用高温熔液法在开放体系生长出高质量的单晶,这些结果表明Na2B6O9F2是一种有前景的深紫外双折射晶体。Na3B7O11F2结晶于正交晶系,空间群为Pnma,晶胞参数为a = 9.259(5) ?,b = 16.337(9) ?,c = 6.634(4) ?,Z = 4,V = 1003.4(9) ?3。Na3B7O11F2晶体结构具有一维的[B7O11F2]3?链,漫反射光谱表明Na3B7O11F2在紫外-可见-近红外光谱区无明显吸收,并且紫外截止边低于190 nm,通过HSE06评估的带隙为6.98eV,计算的双折射率约为0.05。该晶体的成功合成为在开放体系合成和生长氟硼酸盐晶体提供了有力的证据。2. 提出了一种基于氟硼酸盐阴离子基团的深紫外非线性光学晶体的结构设计策略,采用真空封装的高温固相反应方法获得了Li2B6O9F2单晶。Li2B6O9F2结晶于单斜晶系,空间群为Cc,晶胞参数为a = 4.8138(7) ?,b = 16.171(2) ?,c = 10.0611(14) ?,β = 91.961(9) °,Z = 4,V = 782.73(19) ?3。Li2B6O9F2的紫外截止边低于190 nm,在1064和532 nm均能实现Ⅰ类相位匹配,其倍频效应分别约为一倍的KDP@1064 nm和三分之一的BBO@532 nm,并且其计算的双折射率为0.07@1064 nm。这些结果表明Li2B6O9F2是一种非常具有应用前景的深紫外非线性光学晶体材料。本研究对设计和合成深紫外非线性光学晶体有一定的指导意义。

其他摘要

Deep ultraviolet(DUV) optical crystals are critical components in optical communications and laser systems. For example, DUV birefringent crystals have important applications in optical isolator, optical polarizer, 193 nm photolithography, UV spectrophotometers, DUV Raman spectroscopy and fluorescence spectroscopy; DUV nonlinear optical crystals can be applicated in the semiconductor processing industry, ultra-high resolution photoelectron spectroscopy and laser lithography. Therefore, the DUV optical crystal has become a hot spot in the field of material research. This paper is devoted to the design and synthesis of optical crystals that can be applied to DUV region. Considering the problem of the transmission of the optical crystal in the DUV region, we introduce fluorion, the ion with the largest electronegativity, into the borate structure, and choose alkali metal cation without d-d or f-f electron transition to form an alkali metal fluoroborate which facilitates the transmission of DUV light. Alkali metal fluoroborates have relatively short UV absorption cut-off edges, while the polar [BOF] groups aligned in the crystal structure can produce large optical anisotropy and favor a large birefringence. In this paper, the synthesis strategy of alkali metal fluoroborate was put forward. Three alkali metal fluoroborates were synthesized by solid state method, successfully. The characterization and theoretical analysis of these three crystals were carried out, and the main contents are as follows:1. Na2B6O9F2 and Na3B7O11F2 were synthesized by solid-state method, and single crystals were grown by spontaneous crystallization method. Na2B6O9F2 crystallizes in the monoclinic space group P21/c, with unit cell parameters a = 8.1964 (12) ?, b = 13.0005 (19) ?, c = 7.8955 (11) ?, β = 90.750 (2) °, Z = 4, and V = 841.3 (2) ?3. The anionic skeleton of the crystal structure is a two-dimensional [B6O9F2]2– layer. The diffuse reflectance and transmittance spectram show that there is not evident absorption in the UV-vis-NIR region, and the UV absorption cutoff edge is 169 nm. The refractive index of the crystal was measured and the results showed that the birefringence at 589.3 nm was not less than 0.08. It has stable physical and chemical properties, and high-quality single crystal can be grown by high temperature solution method in the open system. These results indicate that Na2B6O9F2 is a potential birefringent material that can be used in DUV region. Na3B7O11F2 crystallizes in orthorhombic system space group Pnma with unit cell parameters a = 9.259 (5) ?, b = 16.337 (9) ?, c = 6.634 (4) ?, Z = 4, V = 1003.4 (9) ?3. The crystal structure has a one-dimensional [B7O11F2]3– chain, and the diffuse reflectance spectrum shows that Na3B7O11F2 has no evident absorption in the UV-vis-NIR spectral region and the UV absorption cutoff edge is below 190 nm. The band gap assessed by HSE06 is 6.98 eV, and the calculated birefringence is about 0.05. The successful synthesis of Na3B7O11F2 in the current work shed some lights in the synthesis of fluoroborates in open systems.2. We propose a structural design strategy for DUV nonlinear optical crystalsbased on fluoroborate group [BOF]. Single crystals of Li2B6O9F2 was synthesized by a vacuum packaging high temperature solid phase reaction method. Li2B6O9F2 crystallizes in monoclinic system space group Cc with unit cell parameters a = 4.8138(7),b = 16.171(2),c = 10.0611(14),β = 91.961(9) °,Z = 4,and V = 782.73(19) ?3. The fundamental building block of Li2B6O9F2 is [B6O9F2]2– group. The UV cut-off edge of Li2B6O9F2 is lower than 190 nm, and class Ⅰ phase matching can be achieved at 1064 and 532 nm. The frequency-doubled effect is about twice as much as KDP @1064 nm and one third of BBO @532 nm, and the calculated birefringence is 0.07@1064 nm. These indicate that Li2B6O9F2 is a very promising DUV nonlinear optical crystal. This study has some implications for the design and synthesis of deep ultraviolet nonlinear optical crystals

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4955
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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史国强. 碱金属氟硼酸盐深紫外光学晶体的合成与性质研究[D]. 北京. 中国科学院大学,2017.
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