Citation: Zhuang LI, Ji-Yong YAO, Yi-Cheng WU. Design and Exploratory Synthesis of Infrared Nonlinear Optical Metal Chalcogenides: Recent Advances and Future Perspectives[J]. Chinese Journal of Structural Chemistry, ;2020, 39(9): 1559-1563. doi: 10.14102/j.cnki.0254-5861.2011-2959 shu

Design and Exploratory Synthesis of Infrared Nonlinear Optical Metal Chalcogenides: Recent Advances and Future Perspectives

Zhuang LI ^{a, b} ,
Ji-Yong YAO ^{a, b,,} ,
Yi-Cheng WU ^c

a.
Beijing Center for Crystal Research and Development, Key Lab of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
c.
Institute of Functional Crystal Materials, Tianjin University of Technology, Tianjin 300384, China

Corresponding author: Ji-Yong YAO, jyao@mail.ipc.ac.cn
Received Date: 11 August 2020
Accepted Date: 27 August 2020

Fund Project: the National Natural Science Foundation of China 51890862the National Natural Science Foundation of China 61675212

Figures(1)

Design and exploratory synthesis of novel infrared nonlinear optical chalcogenides have drawn extensive concerns owing to their excellent overall performance and important role in laser industry. During the past decades, a large number of infrared nonlinear optical chalcogenides have been developed and many effective design strategies have been summarized, which illuminates the path of future explorations. In this perspective, we discuss the feasibility and effectiveness of the representative design ideas. Moreover, we point out some topics to be investigated and discuss the future research directions.
- metal chalcogenide,
- design,
- exploratory synthesis,
- nonlinear optical
1. [1]
  Luo, X.; Li, Z.; Guo, Y.; Yao, J.; Wu, Y. Recent progress on new infrared nonlinear optical materials with application prospect. J. Solid State Chem. 2019, 270, 674–687. doi: 10.1016/j.jssc.2018.12.036
2. [2]
  Liang, F.; Kang, L.; Lin, Z.; Wu, Y. Mid-infrared nonlinear optical materials based on metal chalcogenides: structure-property relationship. Cryst. Growth Des. 2017, 17, 2254–2289. doi: 10.1021/acs.cgd.7b00214
3. [3]
  Wang, S.; Zhan, M.; Wang, G.; Xuan, H.; Zhang, W.; Liu, C.; Xu, C.; Liu, Y.; Wei, Z.; Chen, X. 4H-SiC: a new nonlinear material for midinfrared lasers. Laser Photonics Rev. 2013, 7, 831–838. doi: 10.1002/lpor.201300068
4. [4]
  Wang, G.; Wang, W.; Peng, T.; Guo, L.; Chen, X. Silicon carbide: a wide-bandgap semiconductor and beyond. Science 2018, 360, 51–54.
5. [5]
  Fan, H. T.; Xu, C. H.; Wang, Z. H.; Wang, G.; Liu, C. J.; Liang, J. K.; Chen, X. L.; Wei, Z. Y. Generation of broadband 17-mJ mid-infrared femtosecond pulses at 375 μm by silicon carbide crystal. Opt. Lett. 2014, 39, 6249. doi: 10.1364/OL.39.006249
6. [6]
  Huang, C.; Mao, M.; Wu, H.; Ma, J. Pressure-assisted method for the preparations of high-quality AaGaS₂ and AgGaGeS₄ crystals for mid-infrared laser applications. Inorg. Chem. 2018, 57, 14866–14871. doi: 10.1021/acs.inorgchem.8b02626
7. [7]
  Li, Z.; Zhang, S.; Xing, W.; Guo, Y.; Li, C.; Lin, Z.; Yao, J.; Wu, Y. Mixed-metal thiophosphate CuCd₃PS₆: an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture. J. Mater. Chem. C 2020, 8, 5020–5024. doi: 10.1039/D0TC00832J
8. [8]
  Lin, H.; Li, B. X.; Chen, H.; Liu, P. F.; Wu, L. M.; Wu, X. T.; Zhu, Q. L. Sr₅ZnGa₆S₁₅: a new quaternary non-centrosymmetric semiconductor with a 3D framework structure displaying excellent nonlinear optical performance. Inorg. Chem. Front. 2018, 5, 1458–1462. doi: 10.1039/C8QI00322J
9. [9]
  Li, M. Y.; Li, B. X.; Lin, H.; Shi, Y. F.; Ma, Z.; Wu, L. M.; Wu, X. T.; Zhu, Q. L. Ternary mixed-metal Cd₄GeS₆: remarkable nonlinear-optical properties based on a tetrahedral-stacking framework. Inorg. Chem. 2018, 57, 8730–8734. doi: 10.1021/acs.inorgchem.8b01682
10. [10]
  Kang, L.; Zhou, M.; Yao, J.; Lin, Z.; Wu, Y.; Chen, C. Metal thiophosphates with good mid-infrared nonlinear optical performances: a first-principles prediction and analysis. J. Am. Chem. Soc. 2015, 137, 13049–13059. doi: 10.1021/jacs.5b07920
11. [11]
  Zhou, A.; Lin, C.; Lin, C.; Li, B.; Cheng, W.; Guo, Z.; Guo, Z.; Hou, Z.; Yuan, F.; Chai, G. L. Ba₆In₆Zn₄Se₁₉: a high performance infrared nonlinear optical crystal with [InSe₃]^3- trigonal planar functional motifs. J. Mater. Chem. C 2020, 8, 7947–7955. doi: 10.1039/D0TC01282C
12. [12]
  Chen, M. C.; Wu, L. M.; Lin, H.; Zhou, L. J.; Chen, L. Disconnection enhances the second harmonic generation response: synthesis and characterization of Ba₂₃Ga₈Sb₂S₃₈. J. Am. Chem. Soc. 2012, 134, 6058–6060. doi: 10.1021/ja300249n
13. [13]
  Luo, Z. Z.; Lin, C. S.; Cui, H. H.; Zhang, W. L.; Zhang, H.; Chen, H.; He, Z. Z.; Cheng, W. D. PbGa₂MSe₆ (M = Si, Ge): two exceptional infrared nonlinear optical crystals. Chem. Mater. 2015, 27, 914–922. doi: 10.1021/cm504195x
14. [14]
  Syrigos, J. C.; Clark, D. J.; Saouma, F. O.; Clarke, S. M.; Fang, L.; Jang, J. I.; Kanatzidis, M. G. Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb₂PSe₁₀ (A = K, Rb, and Cs). Chem. Mater. 2015, 27, 255–265. doi: 10.1021/cm5038217
15. [15]
  Chen, M. C.; Li, L. H.; Chen, Y. B.; Chen, L. In-phase alignments of asymmetric building units in Ln₄GaSbS₉ (Ln = Pr, Nd, Sm, Gd-Ho) and their strong nonlinear optical responses in middle IR. J. Am. Chem. Soc. 2011, 133, 4617–4624. doi: 10.1021/ja1111095
16. [16]
  Guo, Y.; Liang, F.; Yin, W.; Li, Z.; Luo, X.; Lin, Z. S.; Yao, J.; Mar, A.; Wu, Y. BaHgGeSe₄ and SrHgGeSe₄: two new Hg-based infrared nonlinear optical materials. Chem. Mater. 2019, 31, 3034–3040. doi: 10.1021/acs.chemmater.9b01023
17. [17]
  Hu, X. N.; Xiong, L.; Wu, L. M. Six new members of the A₂M^IIM₃^IVQ₈ family and their structural relationship. Cryst. Growth Des. 2018, 18, 3124–3131. doi: 10.1021/acs.cgd.8b00247
18. [18]
  Lin, H.; Wei, W. B.; Chen, H.; Wu, X. T.; Zhu, Q. L. Rational design of infrared nonlinear optical chalcogenides by chemical substitution. Coord. Chem. Rev. 2020, 406, 213150. doi: 10.1016/j.ccr.2019.213150
19. [19]
  Chen, C.; Li, R. The anionic group theory of the non-linear optical effect and its applications in the development of new high-quality NLO crystals in the borate series. Int. Rev. Phys. Chem. 1988, 8, 65–91.
20. [20]
  Banerjee, S.; Malliakas, C. D.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G. 1/∞[ZrPSe^6-]: a soluble photoluminescent inorganic polymer and strong second harmonic generation response of its alkali salts. J. Am. Chem. Soc. 2008, 130, 12270–12272. doi: 10.1021/ja804166m
21. [21]
  Zhou, M.; Yang, Y.; Guo, Y.; Lin, Z.; Yao, J.; Wu, Y.; Chen, C. Hg-based infrared nonlinear optical material KHg₄Ga₅Se₁₂ exhibits good phase-matchability and exceptional second harmonic generation response. Chem. Mater. 2017, 29, 7993–8002. doi: 10.1021/acs.chemmater.7b03143
22. [22]
  Liu, B. W.; Zeng, H. Y.; Jiang, X. M.; Wang, G. E.; Li, S. F.; Xu, L.; Guo, G. C. [A₃X][Ga₃PS₈] (A = K, Rb; X = Cl, Br): promising IR non-linear optical materials exhibiting concurrently strong second-harmonic generation and highlaser induced damage thresholds. Chem. Sci. 2016, 7, 6273–6277. doi: 10.1039/C6SC01907B
23. [23]
  Zhou, H. M.; Xiong, L.; Chen, L.; Wu, L. M. Dislocations that decrease size mismatch within the lattice leading to ultrawide band gap, large second-order susceptibility, and high nonlinear optical performance of AgGaS₂. Angew. Chemie - Int. Ed. 2019, 58, 9979–9983. doi: 10.1002/anie.201903976
24. [24]
  Li, Z.; Zhang, S.; Huang, Z.; Zhao, L. D.; Uykur, E.; Xing, W.; Lin, Z.; Yao, J.; Wu, Y. Molecular construction from AgGaS₂ to CuZnPS₄: defect-induced second harmonic generation enhancement and cosubstitution-driven band gap enlargement. Chem. Mater. 2020, 32, 3288–3296. doi: 10.1021/acs.chemmater.0c00609
25. [25]
  Feng, J. H.; Hu, C. L.; Xu, X.; Li, B. X.; Zhang, M. J.; Mao, J. G. AgGa₂PS₆: a new mid-infrared nonlinear optical material with a high laser damage threshold and a large second harmonic generation response. Chem. - A Eur. J. 2017, 23, 10978–10982. doi: 10.1002/chem.201702632
1. [1]
  Ruiyan CHEN , Yanping HE , Jian ZHANG . Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2149-2156. doi: 10.11862/CJIC.20250177
2. [2]
  Huijian Zhao , Jie Song , Shuaifeng Li , Xianghao Kong , Conggang Li , Ning Ye , Zhanggui Hu . Design of rare earth borate short-wave UV nonlinear optical crystals with strengthened second harmonic generation activities via cationic modification strategy. Chinese Chemical Letters, 2026, 37(6): 111011-. doi: 10.1016/j.cclet.2025.111011
3. [3]
  Xiantan Lin , Yicong Lv , Xiaoqi Li , Zengshan Yue , Kai Li , Qingyin Wei , Qianxi Wang , Junhua Luo , Xitao Liu . Rational design of a high-efficiency lead halide organic-inorganic hybrid nonlinear optical switch via molecular engineering. Chinese Chemical Letters, 2026, 37(7): 111083-. doi: 10.1016/j.cclet.2025.111083
4. [4]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
5. [5]
  Yidan Chen , Yan Xiao , Yumiao Niu , Chu Chu , Ying Wang , Daqing Yang , Bingbing Zhang . Computer-aided search and targeted synthesis of infrared nonlinear optical materials in tin-containing sulfides. Chinese Journal of Structural Chemistry, 2026, 45(5): 100885-100885. doi: 10.1016/j.cjsc.2026.100885
6. [6]
  Jiajing Wu , Ru-Ling Tang , Sheng-Ping Guo . Three types of promising functional building units for designing metal halide nonlinear optical crystals. Chinese Journal of Structural Chemistry, 2024, 43(6): 100291-100291. doi: 10.1016/j.cjsc.2024.100291
7. [7]
  Ming-Chang Wang , Zhi Lin , Jia-Jia Li , Jia-Min Lian , Yun-Xia Hu , Yan Chen , Ke-Zhao Du , Jin Chen . Bromine for iodine: Unlocking short-wavelength UV phase matching in nonlinear optical metal halides. Chinese Chemical Letters, 2026, 37(10): 111639-. doi: 10.1016/j.cclet.2025.111639
8. [8]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
9. [9]
  Chengye Lou , Yu Hu , Yunjia Jiang , Lingyao Wang , Yuanbin Zhang . Borane cage hybrid supramolecular metal-organic frameworks (BSFs): Design, synthesis and gas separation performance. Chinese Journal of Structural Chemistry, 2026, 45(2): 100789-100789. doi: 10.1016/j.cjsc.2025.100789
10. [10]
  Ying Zhao , Yin-Hang Chai , Meng-Meng Zhai , Qin-Ying Jin , Xiaoyan Lu , Yi-Dan Qiao , Lu-Fang Ma . New functional metal–organic framework (MOF) based optical thermometer by the post-synthesis doping rare earth ions into MOF. Chinese Chemical Letters, 2026, 37(1): 111085-. doi: 10.1016/j.cclet.2025.111085
11. [11]
  Wenyi Mei , Lijuan Xie , Xiaodong Zhang , Cunjian Shi , Fengzhi Wang , Qiqi Fu , Zhenjiang Zhao , Honglin Li , Yufang Xu , Zhuo Chen . Design, synthesis and biological evaluation of fluorescent derivatives of ursolic acid in living cells. Chinese Chemical Letters, 2024, 35(5): 108825-. doi: 10.1016/j.cclet.2023.108825
12. [12]
  Yanye Fan , Jingjing Chen , Bichun Chen , Jinyu Bai , Bowen Yang , Feng Liang , Lijing Fang . Design, synthesis and biological evaluation of Leu₁₀-teixobactin analogues. Chinese Chemical Letters, 2025, 36(4): 110075-. doi: 10.1016/j.cclet.2024.110075
13. [13]
  Bin Yao , Yao Bu , Hongfei Sun , Guowang Li , Xianying Wu , Wei Wang . Interlocked covalent organic cages: Design, synthesis, and self-assembly. Chinese Chemical Letters, 2026, 37(1): 111894-. doi: 10.1016/j.cclet.2025.111894
14. [14]
  Lihua Gao , Yinglei Han , Chensheng Lin , Huikang Jiang , Guang Peng , Guangsai Yang , Jindong Chen , Ning Ye . Halogen-assisted octet binding electrons construction of pnictogens towards wide-bandgap nonlinear optical pnictides. Chinese Chemical Letters, 2024, 35(12): 109529-. doi: 10.1016/j.cclet.2024.109529
15. [15]
  Hongyuan Sha , Dongling Yang , Yanran Shang , Zujian Wang , Rongbing Su , Chao He , Xiaoming Yang , Xifa Long . Trithionic guanidine: A novel semi-organic short-wave ultraviolet nonlinear optical sulfate with dimeric heteroleptic tetrahedra. Chinese Chemical Letters, 2025, 36(4): 109730-. doi: 10.1016/j.cclet.2024.109730
16. [16]
  Yangfeifei Ou , Xiao-Liang Zhou , You-Zhao Lan , Jian-Wen Cheng . Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions. Chinese Journal of Structural Chemistry, 2025, 44(9): 100708-100708. doi: 10.1016/j.cjsc.2025.100708
17. [17]
  Yijia Chen , Wendan Luo , Ke Liu , Taihong Liu , Liping Ding , Yu Fang . Diverse roles of indacenodithiophene in push-pull chromophores for enhanced two-photon absorption and efficient nonlinear optical limiting. Chinese Journal of Structural Chemistry, 2025, 44(10): 100704-100704. doi: 10.1016/j.cjsc.2025.100704
18. [18]
  Ying Xu , Yan Pu , Qiong Zhang , Xi Kang , Manzhou Zhu . Order-by-order control over the nonlinear optical properties of atomically precise nanoclusters. Chinese Journal of Structural Chemistry, 2025, 44(10): 100735-100735. doi: 10.1016/j.cjsc.2025.100735
19. [19]
  Li Zhou , Fengyu Li , Zhou Lu , Yingwei Wang , Jun He . Two-dimensional atomic crystals for third-order nonlinear optical modulation. Chinese Journal of Structural Chemistry, 2026, 45(2): 100772-100772. doi: 10.1016/j.cjsc.2025.100772
20. [20]
  Le Ye , Zi-Luo Fang , Ming-Yu Guo , Wei-Xiong Zhang . Hot-pressing boosted nonlinear optical properties in a new ferroelectric plastic crystalline material. Chinese Chemical Letters, 2026, 37(4): 110826-. doi: 10.1016/j.cclet.2025.110826

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(2111)
HTML views(95)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142