Citation: 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[J]. Chinese Chemical Letters, ;2026, 37(6): 111011. doi: 10.1016/j.cclet.2025.111011 shu

Design of rare earth borate short-wave UV nonlinear optical crystals with strengthened second harmonic generation activities via cationic modification strategy

Huijian Zhao ^{a, 1} ,
Jie Song ^{a, 1} ,
Shuaifeng Li ^a ,
Xianghao Kong ^a ,
Conggang Li ^{a, *,} ,
Ning Ye ^a ,
Zhanggui Hu ^{a, b, *,}

a.
State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals, Tianjin University of Technology, Tianjin 300384, China
b.
College of Material Science and Engineering, Hefei University of Technology, Hefei 230009, China

cgli@email.tjut.edu.cn

hu@mail.ipc.ac.cn

Received Date: 30 December 2024
Revised Date: 15 February 2025
Accepted Date: 26 February 2025
Available Online: 27 February 2025

Figures(5)

Ultraviolet (UV) nonlinear optical (NLO) crystals have received substantial interest in advanced laser technology. However, tailoring a UV NLO material with a large second harmonic generation (SHG) response and good UV transparency remains a challenge. Here, inspired by the classic A₃-RE₂-[BO₃]₃ parent template, two new rare-earth borate NLO crystals, RbNa₂La₂(BO₃)₃ (RNLBO-Ⅰ) and Rb_0.681Na_2.319La₂(BO₃)₃ (RNLBO-Ⅱ), were extracted by merging larger ionic radius cations Rb⁺ and La³⁺ simultaneously using a chemical substitution-oriented strategy. As expected, both compounds achieve significant enhancements in SHG activities, reaching 4.5 × and 4.3 × KDP, respectively, exceeding three times that of the isomorphic Na₃Gd₂B₃O₉. Notably, RNLBO-Ⅰ displayed the highest SHG response among alkali metal RE-borate NLO crystals containing isolated [BO₃] groups in the short-wave UV region. Moreover, RNLBO-Ⅰ and -Ⅱ demonstrated short UV cutoff edges at 213 and 207 nm, corresponding to wide bandgaps of 5.3 and 5.6 eV, respectively. Additionally, theoretical calculations and dipole moment analysis were conducted to clarify the origin of the enhanced SHG activities of RNLBO-Ⅰ and -Ⅱ. The optimal balance between SHG intensity and UV transparency in RNLBO-Ⅰ and -Ⅱ underscores their potential as UV NLO candidates and offers valuable insights for fabricating new advanced UV NLO materials.
- Rare-earth borates,
- Second harmonic generation,
- Chemical substitution strategy,
- Microscopic polarizability,
- UV nonlinear optical crystals
1. [1]
  P. Halasyamani, J. Rondinelli, Nat. Commun. 9 (2018) 2972. doi: 10.1038/s41467-018-05411-1
2. [2]
  Y. Yang, X. Liu, C. Zhu, et al., Angew. Chem. Int. Ed. 62 (2023) e202301404. doi: 10.1002/anie.202301404
3. [3]
  X. Jiang, M. Zhang, H. Zeng, et al., J. Am. Chem. Soc. 133 (2011) 3410–3418. doi: 10.1021/ja107921a
4. [4]
  C. Pan, X. Yang, L. Xiong, et al., J. Am. Chem. Soc. 142 (2020) 6423–6431. doi: 10.1021/jacs.0c01741
5. [5]
  M. Xia, X. Jiang, Z. Lin, et al., J. Am. Chem. Soc. 138 (2016) 14190–14193. doi: 10.1021/jacs.6b08813
6. [6]
  X. Dong, H. Huang, L. Huang, et al., Angew. Chem. Int. Ed. 63 (2024) e202318976. doi: 10.1002/anie.202318976
7. [7]
  K. Wu, B. Zhang, Z. Yang, et al., J. Am. Chem. Soc. 139 (2017) 14885–14888. doi: 10.1021/jacs.7b08966
8. [8]
  F. Liang, L. Kang, P. Gong, et al., Chem. Mater. 29 (2017) 7098–7102. doi: 10.1021/acs.chemmater.7b03162
9. [9]
  M. Wu, E. Tikhonov, A. Tudi, et al., Adv. Mater. 35 (2023) 2300848. doi: 10.1002/adma.202300848
10. [10]
  B. Zhang, E. Tikhonov, C. Xie, et al., Angew. Chem. Int. Ed. 58 (2019) 11726–11730. doi: 10.1002/anie.201905558
11. [11]
  C. Wu, C. Jiang, G. Wei, et al., J. Am. Chem. Soc. 145 (2023) 3040–3046. doi: 10.1021/jacs.2c11645
12. [12]
  K. Miyazaki, H. Sakai, T. Sato, Opt. Lett. 11 (1986) 797–799. doi: 10.1364/OL.11.000797
13. [13]
  C. Chen, Y. Wu, A. Jiang, et al., J. Opt. Soc. Am. B 6 (1989) 616–621. doi: 10.1364/JOSAB.6.000616
14. [14]
  B. Wu, D. Tang, N. Ye, et al., Opt. Mater. 5 (1996) 105–109. doi: 10.1016/0925-3467(95)00050-X
15. [15]
  W. Wang, D. Mei, S. Wen, et al., Chin. Chem. Lett. 33 (2022) 2301–2315.
16. [16]
  M. Mutailipu, M. Zhang, H. Wu, et al., Nat. Commun. 9 (2018) 3089. doi: 10.1038/s41467-018-05575-w
17. [17]
  M. Mutailipu, K. Poeppelmeier, S. Pan, Chem. Rev. 121 (2021) 1130–1202. doi: 10.1021/acs.chemrev.0c00796
18. [18]
  H. Liu, H. Wu, Z. Hu, et al., J. Am. Chem. Soc. 145 (2023) 12691–12700. doi: 10.1021/jacs.3c02400
19. [19]
  H. Yu, W. Zhang, J. Young, et al., J. Am. Chem. Soc. 138 (2016) 88–91. doi: 10.1021/jacs.5b11712
20. [20]
  L. Gao, Y. Han, C. Lin, et al., Chin. Chem. Lett. 35 (2024) 109529. doi: 10.1016/j.cclet.2024.109529
21. [21]
  G. Zou, K. Ok, Chem. Sci. 11 (2020) 5404–5409. doi: 10.1039/d0sc01936d
22. [22]
  S. Zhao, P. Gong, L. Bai, et al., Nat. Commun. 5 (2014) 4019. doi: 10.1038/ncomms5019
23. [23]
  J. Zhou, Y. Liu, H. Wu, et al., Angew. Chem. Int. Ed. 59 (2020) 19006–19010. doi: 10.1002/anie.202008346
24. [24]
  B. Zhang, G. Shi, Z. Yang, et al., Angew. Chem. Int. Ed. 56 (2017) 3916–3919. doi: 10.1002/anie.201700540
25. [25]
  G. Zou, Z. Lin, H. Zeng, et al., Chem. Sci. 9 (2018) 8957–8961. doi: 10.1039/c8sc03672a
26. [26]
  G. Zou, H. Jo, S. Lim, et al., Angew. Chem. Int. Ed. 57 (2018) 8619–8622. doi: 10.1002/anie.201804354
27. [27]
  Y. Song, M. Luo, F. Liang, et al., Chem. Commun. 54 (2018) 1445–1448. doi: 10.1039/c7cc08863a
28. [28]
  G. Zhang, Y. Wu, P. Fu, et al., Chem. Lett. 30 (2001) 456–457. doi: 10.1246/cl.2001.456
29. [29]
  W. Zhou, R. Zhuang, W. Zhao, et al., Cryst. Res. Technol. 46 (2011) 926–930. doi: 10.1002/crat.201100077
30. [30]
  Y. Liu, X. Liu, S. Liu, et al., Angew. Chem. Int. Ed. 59 (2020) 7793–7796. doi: 10.1002/anie.202001042
31. [31]
  G. Peng, C. Lin, H. Fan, et al., Angew. Chem. Int. Ed. 60 (2021) 17415–17418. doi: 10.1002/anie.202105777
32. [32]
  M. Luo, F. Liang, Y. Song, et al., J. Am. Chem. Soc. 140 (2018) 6814–6817. doi: 10.1021/jacs.8b04333
33. [33]
  J. Song, C. Li, J. Jiao, et al., Inorg. Chem. Front. 10 (2023) 5488–5495. doi: 10.1039/d3qi01004j
34. [34]
  J. Song, H. Zhao, C. Li, et al., Chem. Sci. 15 (2024) 16196–16204. doi: 10.1039/d4sc05081a
35. [35]
  P. Kubelka, F. Munk, Z. Tech. Phys. 12 (1931) 259–274.
36. [36]
  J. Song, C. Hu, X. Xu, et al., Angew. Chem. Int. Ed. 54 (2015) 3679–3682. doi: 10.1002/anie.201412344
37. [37]
  J. Liu, Y. Chen, M. Sun, et al., Cryst. Growth Des. 24 (2024) 2343–2348. doi: 10.1021/acs.cgd.3c01122
38. [38]
  X. Long, R. An, Y. Lv, et al., Chem. Eur. J. 30 (2024) e202401488. doi: 10.1002/chem.202401488
39. [39]
  S. Kurtz, T. Perry, J. Appl. Phys. 39 (1968) 3798–3813. doi: 10.1063/1.1656857
40. [40]
  R. Godby, M. Schlüter, L. Sham, Phys. Rev. B 37 (1988) 10159–10175. doi: 10.1103/PhysRevB.37.10159
41. [41]
  S. Clark, M. Segall, C. Pickard, et al., Z. Kristallogr. 220 (2005) 567–570. doi: 10.1524/zkri.220.5.567.65075
42. [42]
  J. Song, X. Kong, C. Li, et al., Inorg. Chem. 63 (2024) 14786–14793. doi: 10.1021/acs.inorgchem.4c02759
1. [1]
  Juan Chen , Jin-Ni Zhao , Guo-Yu Yang . Four zinc borates: From acentric chain to centric porous layer. Chinese Journal of Structural Chemistry, 2026, 45(2): 100788-100788. doi: 10.1016/j.cjsc.2025.100788
2. [2]
  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
3. [3]
  Zhiwei Sun , Bingbing Wu , Xiaoli Wang , Qingran Ding , Yanqiu Zhang , Xinjie Zhou , Sinan Tan , Ming Zhong , Sangen Zhao , Junhua Luo . Enhancing birefringence and second-harmonic generation response via aliovalent metal substitution. Chinese Journal of Structural Chemistry, 2026, 45(2): 100790-100790. doi: 10.1016/j.cjsc.2025.100790
4. [4]
  Yongjing Deng , Feiyang Li , Zijian Zhou , Mengzhu Wang , Yongkang Zhu , Jianwei Zhao , Shujuan Liu , Qiang Zhao . Chiral induction and Sb³⁺ doping in indium halides to trigger second harmonic generation and circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(8): 109085-. doi: 10.1016/j.cclet.2023.109085
5. [5]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
6. [6]
  Qi Sun , Hongshan Wang , Linlin Liu , Zuxin Chen , Junjie Li , Shilie Pan . A new selenide semiconductor NaMn₃Ga₃Se₈ with strong second-harmonic generation and significant luminescence property. Chinese Journal of Structural Chemistry, 2025, 44(6): 100591-100591. doi: 10.1016/j.cjsc.2025.100591
7. [7]
  Hongdao LI , Shengjian ZHANG , Hongmei DONG . Magnetic relaxation and luminescent behavior in nitronyl nitroxide-based annuluses of rare-earth ions. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 972-978. doi: 10.11862/CJIC.20230411
8. [8]
  Jing Zhang , Lichao Ning , Yong Qiu , Minghui Ji , Shiyu Wang , Yuji Wang , Fei Wang , Xiaoming Feng , Shunxi Dong . Enantioselective intramolecular C–H alkylation of pyridine derivatives with alkene by rare-earth catalysts: Facile synthesis of chiral tetrahydro-1,5-naphthyridines. Chinese Chemical Letters, 2026, 37(5): 111442-. doi: 10.1016/j.cclet.2025.111442
9. [9]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
10. [10]
  Yu Zhou , Lin-Tao Jiang , Xiao-Ming Jiang , Bin-Wen Liu , Guo-Cong Guo . Mixed-anion square-pyramid [SbS₃I₂] units causing strong second-harmonic generation intensity and large birefringence. Chinese Chemical Letters, 2025, 36(4): 109740-. doi: 10.1016/j.cclet.2024.109740
11. [11]
  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
12. [12]
  Lizhi Wang , Chuanxin Wei , Xinyu Du , Yingying Zheng , Shuang Li , Ning Sun , Zhiqiang Zhuo , Ningning Yu , Yingru Lin , Zhiyang Sun , Jinyi Lin , Man Xu , Yongzheng Chang , Tianshi Qin , Zhoulu Wang , Xuehua Ding , Wei Huang . Energy engineering and mechanical elasticity of molecular crystals via supramolecular salt strategy for flexible visible optical waveguide. Chinese Chemical Letters, 2026, 37(2): 111634-. doi: 10.1016/j.cclet.2025.111634
13. [13]
  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
14. [14]
  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
15. [15]
  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
16. [16]
  Haodong Wang , Xiaoxu Lai , Chi Chen , Pei Shi , Houzhao Wan , Hao Wang , Xingguang Chen , Dan Sun . Novel 2D bifunctional layered rare-earth hydroxides@GO catalyst as a functional interlayer for improved liquid-solid conversion of polysulfides in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108473-. doi: 10.1016/j.cclet.2023.108473
17. [17]
  Xiaodong Zhang , Bohui Xu , Deshuai Xiao , Xinyuan Zhang , Pifu Gong , Zheshuai Lin . From centrosymmetric CN3H6C6H5SO3 to non-centrosymmetric CN3H6C6H4SO3(OH): Hydroxyl introduced hydrogen bond reconstruction to realize strong second harmonic generation. Chinese Journal of Structural Chemistry, 2025, 44(10): 100707-100707. doi: 10.1016/j.cjsc.2025.100707
18. [18]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
19. [19]
  Yuwei Kang , Can Yang , Jun Zhang , Qi Wu . Synergistic triple-site engineering in ABX₃-type hybrid halides for high-performance nonlinear optical crystals. Chinese Chemical Letters, 2026, 37(1): 111385-. doi: 10.1016/j.cclet.2025.111385
20. [20]
  Shuang Zhao , Fei Jia , Kaibei Zhan , Rui-Xi Wang , Pengfei Tan , Lin Shen , Li-Ming Wu , Ling Chen . Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A₂(H₃C₃N₄S₂)₂•H₂O (A =NH₄, K, Rb, Cs). Chinese Chemical Letters, 2026, 37(3): 110625-. doi: 10.1016/j.cclet.2024.110625

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(18)
HTML views(2)

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