Vacancy-driven tetrahedral distortion leading to exceptional second harmonic generation

IF 7.4 2区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Science China Materials Pub Date : 2025-09-03 DOI:10.1007/s40843-025-3500-x

Weiping Guo (, ), Yongjia Zhang (, ), Hong-Hua Cui (, ), Xin-Xiong Li (, ), Lingyun Li (, ), Yan Yu (, ), Zhong-Zhen Luo (, ), Zhigang Zou (, )

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引用次数: 0

Abstract

In this work, cation vacancies induced the tetrahedral distortion, enhancing the second harmonic generation (SHG) response in the diamond-like (DL) structure compounds. Concretely, the high valence and electronegativity of P⁵⁺ were introduced to substitute the Ge⁴⁺ in Cd₄GeS₆, which shows a general SHG response of 1.1 × AgGaS₂ (AGS) at 2050 nm. Thus, the isomorphic defective DL Cd_3.5PS₆ was obtained with inherent Cd²⁺ vacancies, leading to an 8.5-fold increase in [CdS₄] tetrahedral distortion degree than Cd₄GeS₆. As a result, Cd_3.5PS₆ has a high SHG response of 2 × AGS at 2050 nm and a laser-induced damage threshold (LIDT) of 9.4 × AGS. Furthermore, equivalent Hg²⁺ substitution concentrates Cd²⁺ vacancies at the Cd(2) site, leading to a 2.66-fold [CdS₄] tetrahedral distortion degree than Cd_3.5PS₆. Consequently, Hg_0.5Cd₃PS₆ possesses a high SHG response of 2.73 × AGS at 2050 nm and LIDT of 5 × AGS with a birefringence of 0.076@2050 nm. The results indicate that the cation vacancies and radius scale of mixed atoms provide effective ways to design high-performance nonlinear optical crystals.

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空位驱动的四面体畸变导致异常的二次谐波产生

在这项工作中，阳离子空位诱导了四面体畸变，增强了类金刚石结构化合物的二次谐波产生（SHG）响应。在Cd4GeS6中引入P5+的高价位和电负性取代Ge4+，在2050 nm处表现出1.1 × AgGaS2 （AGS）的SHG响应。因此，获得了具有固有Cd2+空位的同构缺陷DL Cd3.5PS6，导致[CdS4]四面体畸变程度比Cd4GeS6增加8.5倍。结果表明，Cd3.5PS6在2050 nm具有2 × AGS的高SHG响应，激光诱导损伤阈值（LIDT）为9.4 × AGS。此外，等效的Hg2+取代将Cd2+空位集中在Cd(2)位点上，导致[CdS4]四面体畸变程度是Cd3.5PS6的2.66倍。因此，Hg0.5Cd3PS6在2050 nm处具有2.73 × AGS的高SHG响应，LIDT为5 × AGS，双折射为0.076@2050 nm。结果表明，混合原子的阳离子空位和半径尺度为设计高性能非线性光学晶体提供了有效途径。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science China Materials Materials Science-General Materials Science

CiteScore

11.40

自引率

7.40%

发文量

949

期刊介绍： Science China Materials (SCM) is a globally peer-reviewed journal that covers all facets of materials science. It is supervised by the Chinese Academy of Sciences and co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China. The journal is jointly published monthly in both printed and electronic forms by Science China Press and Springer. The aim of SCM is to encourage communication of high-quality, innovative research results at the cutting-edge interface of materials science with chemistry, physics, biology, and engineering. It focuses on breakthroughs from around the world and aims to become a world-leading academic journal for materials science.