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Recent advances in non-π-conjugated nonlinear optical sulfates with deep-UV absorption edge

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Chinese Journal of Structural Chemistry 2023年第3期42卷 56-63页

作者： Xu Chen Yanqiang Li Junhua Luo sangen zhao College of Chemistry Fuzhou UniversityFuzhouFujian350108China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian350002China University of Chinese Academy of Sciences Beijing100049China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China FuzhouFujian350108China

Deep-ultraviolet(deep-UV)nonlinear optical(NLO)crystals are of current interest because they play an indis-pensable role in modern scientific *** these crystals was traditionally limited toπ-conjugated systems,such as borates and *** 2019,our group reported two non-π-conjugated sulfates as new sources of deep-UV NLO crystals for the first *** this mini review,we provide a comprehensive overview of the recent development of non-π-conjugated NLO sulfates with deep-UV absorption edge in aspect of synthesis methods,crystal structures,thermal stability,and optical ***,we conclude the crucial structure-property relationships,and further give some prospects for exploring non-π-conjugated NLO sulfates with deep-UV absorption edge with high thermal stability,enhanced second-order NLO effects,birefringence,*** believe that this mini review will not only facilitate researchers to design superior non-π-conjugated NLO sulfates with deep-UV absorption edge but also shed useful insights on the explorations of other non-π-conjugated deep-UV NLO crystal systems.

关键词： Crystal structures Structure-property relationships Deep-UV NLO crystals Sulfates

Designing a deep-UV nonlinear optical monofluorophosphate

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Science China Chemistry 2022年第9期65卷 1710-1714页

作者： Qingran Ding Xingyu Zhang Zheshuai Lin Zheyao Xiong Yusong Wang Xifa Long sangen zhao Maochun Hong Junhua Luo School of Chemistry and Chemical Engineering Jiangxi Normal UniversityNanchang 330022China Fujian Institute of Research on the Structure of Matter Chinese Academy of SciencesFuzhou 350002China Technical Institute of Physics and Chemistry Chinese Academy of SciencesBeijing 100190China University of Science and Technology of China Hefei 230026China

As structural variants of famous hexagonal tungsten bronzes,hexagonal tungsten oxides(HTO)represent an important family with fascinating functional properties,such as piezoelectric,ferroelectric,pyroelectric,and nonlinear optical(NLO)***,none of them are transparent in the deep-UV spectral region,which limits their ***,we report the first HTO-type monofluorophosphate K_(3)Sc_(3)(PO_(4))(PO_(3)F)_(2)F_(5)(I)with deep-UV *** a monofluorophosphate is NLO-active with a phase-matchable powder second harmonic generation efficiency of 0.9 times that of KH_(2)PO_(4)at 1,064 ***,the UV-Vis reflectance spectrum indicates that it is deep-UV transparent down to 200 *** work pushes the transparent window of NLO materials with HTO-type structures down to the deep-UV spectral region for the first time and opens up a new door for HTO materials.

关键词： monofluorophosphate hexagonal tungsten oxides deep-UV nonlinear optics crystal

A new 2D van der Waals material with air stability and in-plane anisotropy

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Chinese Journal of Structural Chemistry 2023年第7期42卷 9-13页

作者： Han Wang Jinyang Liu Minjuan Li Yanqiang Li Yang Zhou Wei Liu Junhua Luo sangen zhao State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou350002China College of Chemistry and Materials Science Fujian Normal UniversityFuzhou350007China College of Physics and Energy Fujian Normal UniversityFuzhou350117China

*** 2D van der Waals materials possess intriguing features[1],especially optically,such as high nonlinear optical responses[2],broadband spectral response[3],and accessible exciton effects[4].Unlike conventional 2D materials with in-plane isotropy,such as graphene and M0S_(2),2D van der Waals materials with in-plane anisotropic possess in-plane low symmetry structure,inducing the in-plane anisotropic physical ***,they can be easily moved to various substrates without lattice-matching problems.

关键词： properties. plane anisotropic

Noncentrosymmetric K_(2)Mn_(3)(SO_(4))_(3)F_(2)·4H_(2)O and Rb_(2)Mn_(3)(SO_(4))_(3)F_(2)·2H_(2)O with pseudo-KTP structures

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Chinese Chemical Letters 2021年第1期32卷 263-265页

作者： Yang Zhou Yanqiang Li Qingran Ding Youchao Liu Yangxin Chen Xitao Liu Xiaoying Huang Lina Li sangen zhao Junhua Luo College of Chemistry and Materials Science Fujian Normal UniversityFuzhou 350007China State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China

Two fluoride sulfates,K_(2)Mn_(3)(SO_(4))_(3)F_(2)·4H_(2)O(Ⅰ) and Rb_(2)Mn_(3)(SO_(4))_(3)F_(2)·2H_(2)O (Ⅱ) are obtained by water solution ***-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_(1.)Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn_(3)(SO_(4))3F_(2)(H_(2)O)2]_(∞) layers,which are further packing along the a axis with alkali metal cations balancing the *** structure relationships between the two compounds are *** generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH_(2)PO_(4).

关键词： Sulfate Second harmonic generation Crystal structure X-ray diffraction Thermogravimetric analysis

Preface to Nonlinear Optical Crystals

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Chinese Journal of Structural Chemistry 2023年第3期42卷 1-3页

作者： sangen zhao Guohong Zou Min Zhang Hongwei Yu Xingxing Jiang Min Luo Fujian Institute of Research on the Structure of Matter Chinese Academy of SciencesFuzhouChina Sichuan University ChengduChina Xinjiang Technical Institute of Physics and Chemistry Chinese Academy of SciencesUrumqiChina Tianjin University of Technology TianjinChina Technical Institute of Physics and Chemistry Chinese Academy of SciencesBeijingChina

Nonlinear optical(NLO)crystals can efficiently convert the frequency of common solid-state laser with fixed or limited *** the first observation of second-harmonic generation(SHG)phenomenon in the early 1960s,they have played an increasing role in the fields of laser spectra,precision measurements,and quantum information,as well as industrial laser processing,and so ***,it is still challenging to rationally design and synthesize new NLO crystals.

关键词： laser Crystal Nonlinear

Maximizing the linear and nonlinear optical responses of alkaline tricyanomelaminate

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Fundamental Research 2023年第6期3卷 974-978页

作者： Yanqiang Li Qingchen Wu Zheshuai Lin Youchao Liu Yang Zhou Xin Chen Minjuan Li Maochun Hong Junhua Luo sangen zhao State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Technical Institute of Physics and Chemistry Chinese Academy of SciencesBeijing 100190China University of Chinese Academy of Sciences Beijing 100049China Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China

High-performance bi-functional materials are in urgent demand for the next-generation integrated optical *** this work,we successfully synthesized the first tricyanomelaminate with bi-functional optical responses,namely Cs_(3)C_(6)N_(9)•H_(2)O(I),from its analogue Na_(3)C_(6)N_(9)•3H_(2)O by a facile ion exchange *** contrast to Na_(3)C_(6)N_(9)•3H_(2)O,I realizes an optimal arrangement of𝜋π-conjugated(C_(6)N_(9))3−anion groups in its crystal *** a result,the second-order nonlinear optical(NLO)response is greatly enhanced from nearly zero of Na_(3)C_(6)N_(9)•3H_(2)O to∼9.8×KH_(2)PO_(4)of ***,I exhibits a giant linear optical anisotropic response(***)of 0.52 at the wavelength of 550 *** responses are almost the largest among the inorganic compounds ofπ-conjugated rings,which indicates that I has great potential as a bi-functional optical *** and theoretical analyses reveal the microscopic origin of excellent optical *** work would attract a lot of interest to the persistently neglected potential of tricyanomelaminates as linear optical and NLO crystals.

关键词： Nonlinear optical response Second harmonic generation Birefringence Tricyanomelaminate Structure-property relationship Inorganic chemistry

Achieving effective balance between bandgap and birefringence by confining p-conjugation in an optically anisotropic crystal

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Science Bulletin 2022年第22期67卷 2276-2279页

作者： Yang Zhou Xu Zhang Maochun Hong Junhua Luo sangen zhao State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Jiangxi University of Science and Technology Ganzhou 341000China University of the Chinese Academy of Sciences Beijing 100049China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China

Birefringence arises when the propagation speed and refractive index of light in an optically anisotropic crystal changes in response to the direction of ***,birefringence belongs to linear optical anisotropy and is a key parameter for linear optoelectronic functional crystals,such as birefringent crystals,which are widely used to modulate the polarization of light in optoelectronic areas[1].In terms of practical applications,there is still an urgent need for wide-bandgap birefringent crystals as they allow for the modulation of light polarization in short-wavelength UV waves and even in the deep-UV spectral region.

关键词：双折射晶体光隔离器光学各向异性宽带隙限域效应结构单元光学性能溶液法

A Nonlinear Optical Switchable Sulfate of Ultrawide Bandgap

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CCS Chemistry 2021年第7期3卷 2298-2306页

作者： Yanqiang Li Congling Yin Xiaoyan Yang Xiaojun Kuang Jie Chen Lunhua He Qingran Ding sangen zhao Maochun Hong Junhua Luo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002 University of Chinese Academy of Sciences Beijing 100049 MOE Key Laboratory of New Processing Technology for Nonferrous Metals and Materials Guangxi Key Laboratory of Optical and Electronic Materials and DevicesCollege of Materials Science and EngineeringGuilin University of TechnologyGuilinGuangxi 541004 Beijing National Laboratory for Condensed Matter Physics Institute of PhysicsChinese Academy of SciencesBeijing 100190 Songshan Lake Materials Laboratory DongguanGuangdong 523808 Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China FuzhouFujian 350108

Nonlinear optical(NLO)switchable materials have attracted intense attention because of their promising applications in optoelectronic ***,previous studies are mainly limited to molecular-based compounds that usually exhibit narrow ***,we report all-inorganic Li_(9)Na_(3)Rb_(2)(SO_(4))_(7) as an ultrawide-bandgap NLO switchable material.

关键词： ultrawide bandgap NLO optics switchable material phase transition sulfates

Nonpolar Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4) Exhibits a Large Second-Harmonic Generation

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CCS Chemistry 2022年第2期4卷 526-531页

作者： Youchao Liu Youquan Liu Zheshuai Lin Yanqiang Li Qingran Ding Xin Chen Lina Li sangen zhao Maochun Hong Junhua Luo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002 Technical Institute of Physics and Chemistry Chinese Academy of SciencesBeijing 100190 University of the Chinese Academy of Sciences Beijing 100049 Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China FuzhouFujian 350108

Conventional wisdom says that nonpolar structures do not favorably produce strong second-harmonic generation(SHG)responses since the polarization in their microscopic functional groups are ***,we report the first nonlinear optical thiosulfate,Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4),which crystallizes in a nonpolar space group of P−***,this thiosulfate exhibits a strong SHG response of about 4.2 times that of the benchmark KH2PO4,which is larger than those of polar *** to first-principles calculations and a flexible dipole model,the SHG enhancement is mainly ascribed to the larger flexibility of the S=S bond in the SO_(3)S tetrahedra in comparison with the S–O bond in the SO4 *** findings indicate that constructing flexible bonds is an effective strategy to design highperformance nonlinear optical materials regardless of polarity.

关键词： nonlinear optical material secondharmonic generation crystal structure structure-property relationships thiosulfate