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高极化多面体诱导CeF2(SO4)的大二次谐波响应和巨双折射
作者:小柯机器人 发布时间:2021/2/28 18:42:34

同济大学张弛团队首次报道了具有大二次谐波响应和巨双折射的高极化多面体诱导CeF2(SO4)。相关研究成果于2021年2月24日发表于国际一流学术期刊《美国化学会杂志》。

二次谐波(SHG)响应和双折射是非线性光学(NLO)材料的两个重要特性。然而,因为它们的显微结构要求不同,同时优化这两个关键性能仍然是一个主要的挑战。

该文报道了第一种四价稀土金属氟化硫酸盐CeF2(SO4)。它的结构特征是由高度扭曲的[CeO4F4]多面体构成新颖的网状层,这些多面体进一步通过[SO4]四面体相互连接形成三维结构。CeF2(SO4)表现出最强的SHG效应(是KH2PO4的8倍)和最大的双折射,后者超过了氧化物的双折射极限。

理论计算和晶体结构分析表明,这种异常大的倍频响应和巨大的双折射可归因于高极化氟化[CeO4F4]多面体的引入以及[CeO4F4]多面体和[SO4]四面体的良好排列。

该研究为设计合成高性能NLO材料提供了一种新的思路。

附:英文原文

Title: Large Second-Harmonic Response and Giant Birefringence of CeF2(SO4) Induced by Highly Polarizable Polyhedra

Author: Chao Wu, Tianhui Wu, Xingxing Jiang, Zujian Wang, Hongyuan Sha, Lin Lin, Zheshuai Lin, Zhipeng Huang, Xifa Long, Mark G. Humphrey, Chi Zhang

Issue&Volume: February 24, 2021

Abstract: Second-harmonic generation (SHG) response and birefringence are two critically important properties of nonlinear optical (NLO) materials. However, the simultaneous optimization of these two key properties remains a major challenge because of their contrasting microstructure requirements. Herein, we report the first tetravalent rare-earth metal fluorinated sulfate, CeF2(SO4). Its structure features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected by [SO4] tetrahedra to form a three-dimensional structure. CeF2(SO4) exhibits the strongest SHG effect (8 times that of KH2PO4) and the largest birefringence for sulfate-based NLO materials, the latter exceeding the birefringent limit for oxides. Theoretical calculations and crystal structure analysis reveal that the unusually large SHG response and giant birefringence can be attributed to the introduction of the highly polarizable fluorinated [CeO4F4] polyhedra as well as the favorable alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the designed synthesis of high-performance NLO materials.

DOI: 10.1021/jacs.1c00416

Source: https://pubs.acs.org/doi/10.1021/jacs.1c00416

 

期刊信息

JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000