离子替代致使非线性光学效应增益的诱导机制研究

Second order nonlinear optical (NLO) materials are one kind of the most important materials in the field of optoelectronic technology. With the idea of introducing non-centrosymmetry units such as units with the stereochemically active lone pair (SCALP) is one common way to obtain new materials with good NLO effect, we designed and synthesized M2B5O9Cl, M2Ba3B3O9Cl,etc, with SCALP cations by Ba-Pb substitution. However, NLO effect enhancements are apparently different among the borate groups after making Ba to Pb substitution, and not corresponding to SCALP activity. Therefore, aiming in design and synthesis new materials oriented by material functions, the present project will focus on a class of oxysalts. First, to study the induction mechanism of NLO active units from SCALP cations and other factors via experimental and the first-principles methods. Second, to investigate the NLO effect enhancement after making ion-substitution with the help of atom-contribution tracking scheme, and try to find the relationship among electronic structure, crystal structure and macroscopic properties. Third, to explore the strategy of material screening and controllable synthesis based on the studies of NLO active induction mechanism. The implement of the project may offer a novel approach for function-oriented integration design.

二阶非线性光学(NLO)材料是当前光电子技术等领域的核心材料之一，通过引入不对称结构单元如含立体化学活性孤对电子（SCALP）基元是获得NLO材料有效手段。本课题组前期采用离子替换机制初步获得了M2B5O9Cl、M2Ba3B3O9Cl(M=Ba,可引入具有SCALP基元的Pb)等NLO材料，然而离子替换前后NLO效应增益存在显著差异，且并不一一对应SCALP活性。故为能有效进行功能导向性材料设计与制备，本项目重点以一类阳离子替换前后的含氧酸盐材料为研究目标，拟开展：基于实验和第一性原理计算等数值方法，深入研究SCALP阳离子等因素诱导NLO活性机制；进而结合基团贡献追踪方法研究离子替换前后二阶NLO效应增益机制，揭示电子结构-微观结构-宏观性能内禀关联性质；通过NLO活性诱导机制研究，初步探索NLO材料筛选及可控制备方案。项目实施为"NLO效应"、"紫外透过"等功能导向性集成设计提供思路。

二阶非线性光学(NLO)材料是当前光电子技术等领域的核心材料之一，通过引入不对称结构单元如含立体化学活性孤对电子（SCALP）基元是获得 NLO 材料有效手段。本课题组采用离子替换机制获得 M2Ba3B3O9Cl(M=Ba,可引入具有 SCALP基元的Pb)等 NLO材料，然而离子替换前后NLO效应增益存在显著差异，且并不一一对应SCALP活性。故为能有效进行功能导向性材料设计与制备，本项目重点以一类阳离子替换前后的含氧酸盐材料为研究目标，基于实验和第一性原理计算等数值方法，深入研究了SCALP阳离子等因素诱导 NLO 活性机制；进而结合基团贡献追踪方法研究了离子替换前后二阶 NLO 效应增益机制，揭示了电子结构-微观结构-宏观性能内禀关联性质；通过 NLO 活性诱导机制研究，初步探索 NLO 材料筛选及可控制备方案，设计合成出较阳离子不同的同构化合物倍频效应增益达6倍的非线性光学晶体。项目实施为“NLO 效应”、“紫外透过”等功能导向性集成设计提供思路。在该项目支持下，相关成果在J. Am. Chem. Soc.(影响因子=14.203)、Angew. Chem. Int. Ed.（影响因子=12.208）、Chem. Mater.（影响因子=9.8）、Appl. Phys. Lett.（影响因子=3.4）等材料、物理类著名SCI期刊上发表论文20篇，其中作为第一、第二标注SCI论文为14篇，申请中国发明专利2项，该研究成果获得2018年新疆自然科学奖一等奖。