电子离域诱导性能提升的深紫外非线性光学材料模板结构设计研究  

CaBO_(2)F: A novel deep-UV structural template with high nonlinear optical performance induced by electron delocalization

作　　者：屠晨晨 阿布都卡地吐地 靳文琪 谢聪伟 杨志华 Chenchen Tu;Abudukadi Tudi;Wenqi Jin;Congwei Xie;Zhihua Yang(Research Center for Crystal Materials,CAS Key Laboratory of Functional Materials and Devices for Special Environments,Xinjiang Technical Institute of Physics&Chemistry,CAS,Urumqi 830011,China;Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China;Skolkovo Institute of Science and Technology,Skolkovo Innovation Center 121205,Moscow,Russian Federation)

机构地区：[1]Research Center for Crystal Materials,CAS Key Laboratory of Functional Materials and Devices for Special Environments,Xinjiang Technical Institute of Physics&Chemistry,CAS,Urumqi 830011,China [2]Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China [3]Skolkovo Institute of Science and Technology,Skolkovo Innovation Center 121205,Moscow,Russian Federation

出　　处：《Science China Materials》2023年第3期1197-1204,共8页中国科学（材料科学（英文版）

基　　金：supported by the National Key R&D Program of China(2021YFB3601502);the National Natural Science Foundation of China(51922014 and 22193044);the Key Research Program of Frontier Sciences,CAS(ZDBS-LY-SLH035);the West Light Foundation of CAS(2019-YDYLTD-002);the International Partnership Program of CAS(1A1365KYSB20200008);the Natural Science Foundation of Xinjiang(2021D01E05);the CAS Project for Young Scientists in Basic Research(YSBR-024);the Instrument Developing Project of CAS(GJJSTD20200007).

摘　　要：探索具有深紫外相位匹配能力的新型非线性光学材料是当前研究热点.本文从硼氧阴离子框架出发,发现由π共轭BO_(3)基团组成一维(BO_(2))∞链的电子离域导致了极化特性增强,可实现非线性光学性能的优化.据此,本文预测了以(BO_(2))∞链为阴离子框架的CaBO_(2)F体系.重点研究了三种能量最低的结构CaBO_(2)F-Ⅰ,CaBO_(2)F-Ⅱ和CaBO_(2)F-Ⅲ,设计了热力学上可进行的反应路径.第一原理计算表明,CaBO_(2)F-Ⅰ,CaBO_(2)-F-Ⅱ和CaBO_(2)F-Ⅲ具有较宽的带隙,合适的双折射(0.076–0.108@1064 nm)和较大的倍频系数(2.1–2.7×KDP).其中,计算得到CaBO_(2)F-Ⅰ的最短相位匹配波长在约为195 nm(基于HSE06带隙修正剪刀算符),证明了含有定向电子离域的(BO_(2))∞链是深紫外非线性光学材料的潜在阴离子框架.本文通过将机理研究与验证性的结构预测相结合实现了自上而下设计深紫外非线性光学结构模板,该研究为探索新型非线性光学材料提供了新的策略.Nonlinear optical (NLO) materials with deepultraviolet (deep-UV) phase-matching capability are of current interest owing to their applications in photoelectric technology.The anionic framework,including the microscopic unit,arrangement,and connection mode,is vital to optimizing the contradictory NLO performances.Herein,the polarizability characteristics of low-dimensional anionic frameworks were investigated.Results revealed that the oriented electron delocalization in a specific direction enhances the polarization and optimizes the NLO performance.A new borate fluoride system,namely CaBO_(2)F,was designed via topdown structural prediction methods.In this system,CaBO_(2)F-Ⅰ,Ⅱ,and Ⅲ with low energy have one-dimensional (BO_(2))∞anionic frameworks.The first-principles calculations show that CaBO_(2)F-Ⅰ,Ⅱ,and Ⅲ have wide deep-UV band gaps suitable birefringence (0.076–0.108@1064 nm),and large second harmonic generation coefficients (2.1–2.7×KH_(2)PO_(4)(KDP)).Particularly,CaBO_(2)F-Ⅰ has a short phase-matching wavelength of 195 nm (Heyd-Scuseria-Ernzerhof (HSE06))which is the first alkaline earth borate fluoride template with one-dimensional (BO_(2))∞that reaches deep-UV phase-matching capability.This result offers a new guideline for exploring novel NLO materials.

关 键 词：非线性光学材料 电子离域 非线性光学性能 相位匹配 自上而下设计 结构模板 结构预测 反应路径 

分 类 号：O437[机械工程—光学工程] TB34[理学—光学]