Citation: A-Yang Wang, Sheng-Hua Zhou, Mao-Yin Ran, Xin-Tao Wu, Hua Lin, Qi-Long Zhu. Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy[J]. Chinese Chemical Letters, ;2024, 35(10): 109377. doi: 10.1016/j.cclet.2023.109377 shu

Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy

A-Yang Wang ^{a, b, c, 1} ,
Sheng-Hua Zhou ^{a, b, d, 1} ,
Mao-Yin Ran ^{a, b, d} ,
Xin-Tao Wu ^{a, b} ,
Hua Lin ^{a, b, *,} ,
Qi-Long Zhu ^{a, b, *,}

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS), Fuzhou 350002, China
b.
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China
c.
College of Chemistry, Fuzhou University, Fuzhou 350108, China
d.
University of Chinese Academy of Sciences, Beijing 100049, China

linhua@fjirsm.ac.cn

qlzhu@fjirsm.ac.cn

Received Date: 9 November 2023
Revised Date: 4 December 2023
Accepted Date: 6 December 2023
Available Online: 12 December 2023

Figures(4)

Recently, non-centrosymmetric (NCS) Hg-based chalcogenides have garnered significant interest due to their strong second-harmonic-generation intensities (d_eff), making them attractive candidates for infrared nonlinear optical (IR-NLO) application. However, achieving both wide band gaps (E_g) and large phase-matched d_eff simultaneously in these materials remains a challenge due to their inherent constraints on each other. In this research, we have successfully obtained two quaternary NCS Hg-based chalcogenides, Rb₂HgGe₃S₈ and Cs₂HgGe₃S₈, by implementing a bandgap engineering strategy that involves alkali metal introduction and Hg/Ge ratio regulation. Both compounds consist of 2D [HgGe₃S₈]^2– anionic layers made of 1D [HgGeS₆]^6– chains and dimeric [Ge₂S₆]^4– polyhedra arranged alternately, and the charge-balanced Rb⁺/Cs⁺ cations located between these layers. Remarkably, Rb₂HgGe₃S₈ and Cs₂HgGe₃S₈ exhibit overall properties required for promising IR-NLO materials, including sufficient PM d_eff (0.55–0.70 × AgGaS₂@2050 nm), large E_g (3.27–3.41 eV), giant laser-induced damage thresholds (17.4–19.7 × AgGaS₂@1064 nm), broad optical transmission intervals (0.32–17.5 µm), and suitable theoretical birefringence (0.069–0.086@2050 nm). Furthermore, in-depth theoretical analysis reveals that the exceptional IR-NLO performance is attributed to the synergy effects of distorted [HgS₄] and [GeS₄] tetrahedra. Our study provides a useful strategy for enhancing the E_g and advancing Hg-based IR-NLO materials, which is expected to extended and implemented in other chalcogenide systems.
- Hg-based chalcogenides,
- IR nonlinear material,
- Structure-activity relationship,
- Wide energy gap,
- Bandgap engineering strategy
1. [1]
  F.J. Duarte, Chapters 2, 9 and 12, Tunable Laser Applications, CRC Press, Boca Raton, FL, 2008.
2. [2]
  V. Petrov, Prog. Quantum Electron. 44 (2015) 1–106. doi: 10.1016/j.pquantelec.2015.08.002
3. [3]
  V.A. Serebryakov, E.V. Boiko, N.N. Petrishchev, et al., J. Opt.Technol. 77 (2010) 6–17. doi: 10.1364/JOT.77.000006
4. [4]
  X.T. Wu, L. Chen, Struct. Bonding 145 (2012) 1–42.
5. [5]
  N.L.B. Sayson, T. Bi, V. Ng, et al., Nat. Photonics 13 (2019) 701–706. doi: 10.1038/s41566-019-0485-4
6. [6]
  G.D. Boyd, E. Buehler, F.G. Storz, Appl. Phys. Lett. 18 (1971) 301–304. doi: 10.1063/1.1653673
7. [7]
  G.C. Catella, L.R. Shiozawa, J.R. Hietanen, et al., Appl. Opt. 32 (1993) 3948–3951. doi: 10.1364/AO.32.003948
8. [8]
  A. Harasaki, K.J. Kato, Appl. Phys. 36 (1997) 700–703. doi: 10.1143/JJAP.36.700
9. [9]
  L. Kang, M.L. Zhou, J.Y. Yao, et al., J. Am. Chem. Soc. 137 (2015) 13049–13059. doi: 10.1021/jacs.5b07920
10. [10]
  S.P. Guo, Y. Chi, G.C. Guo, Coord. Chem. Rev. 335 (2017) 44–57. doi: 10.1016/j.ccr.2016.12.013
11. [11]
  K. Wu, S.L. Pan, Coord. Chem. Rev. 377 (2018) 191–208. doi: 10.1016/j.ccr.2018.09.002
12. [12]
  H. Lin, W.B. Wei, H. Chen, et al., Coord. Chem. Rev. 406 (2020) 213150. doi: 10.1016/j.ccr.2019.213150
13. [13]
  W.K. Wang, D.J. Mei, F. Liang, et al., Coord. Chem. Rev. 421 (2020) 213444. doi: 10.1016/j.ccr.2020.213444
14. [14]
  M.Y. Ran, A.Y. Wang, W.B. Wei, et al., Coord. Chem. Rev. 481 (2023) 215059. doi: 10.1016/j.ccr.2023.215059
15. [15]
  H. Chen, W.B. Wei, H. Lin, et al., Coord. Chem. Rev. 448 (2021) 214154. doi: 10.1016/j.ccr.2021.214154
16. [16]
  H. Chen, M.Y. Ran, W.B. Wei, et al., Coord. Chem. Rev. 470 (2022) 214706. doi: 10.1016/j.ccr.2022.214706
17. [17]
  W. Zhou, J. Wu, W. Liu, et al., Coord. Chem. Rev. 477 (2023) 214950. doi: 10.1016/j.ccr.2022.214950
18. [18]
  F. Hou, D. M, Y. Zhang, et al., J. Alloys Compd. 904 (2022) 163944. doi: 10.1016/j.jallcom.2022.163944
19. [19]
  M. Ma, J. Dang, Y. Wu, et al., Inorg. Chem. 62 (2023) 6549–6553. doi: 10.1021/acs.inorgchem.3c00683
20. [20]
  C.X. Li, X.H. Meng, Z. Li, et al., Coord. Chem. Rev. 453 (2022) 214328. doi: 10.1016/j.ccr.2021.214328
21. [21]
  W. Xing, C. Tang, P. Gong, et al., Inorg. Chem. 60 (2021) 18370–18378. doi: 10.1021/acs.inorgchem.1c02965
22. [22]
  Y. Guo, F. Liang, Z. Li, et al., Inorg. Chem. 58 (2019) 10390–10398. doi: 10.1021/acs.inorgchem.9b01572
23. [23]
  Y. Guo, F. Liang, W. Yin, et al., Chem. Mater. 31 (2019) 3034–3040. doi: 10.1021/acs.chemmater.9b01023
24. [24]
  X.Y. Zhang, H.P. Wu, Z.G. Hu, et al., Adv. Optical Mater. 11 (2023) 2301735.
25. [25]
  M.Y. Ran, S.H. Zhou, W.B. Wei, et al., Small 20 (2024) 2304563. doi: 10.1002/smll.202304563
26. [26]
  Y. Zhang, H. Wu, Z. Hu, et al., Inorg. Chem. Front. 9 (2022) 4075–4080. doi: 10.1039/D2QI00937D
27. [27]
  W. Xing, C. Tang, N. Wang, B. Kang, et al., Adv. Opt. Mater. 9 (2021) 2100563. doi: 10.1002/adom.202100563
28. [28]
  M.Y. Li, B.X. Li, H. Lin, et al., Inorg. Chem. 57 (2018) 8730–8734. doi: 10.1021/acs.inorgchem.8b01682
29. [29]
  J.D. Chen, C.S. Lin, S.D. Yang, et al., Cryst. Growth Des. 20 (2020) 2489–2496. doi: 10.1021/acs.cgd.9b01649
30. [30]
  J. Serment, G. Perez, P. Hagenmuller, Bull. Soc. Chim. Fr. 2 (1968) 561–566.
31. [31]
  K. Wu, Z. Yang, S. Pan, Chem. Mater. 28 (2016) 2795–2801. doi: 10.1021/acs.chemmater.6b00683
32. [32]
  K. Wu, Z. Yang, S. Pan, Chem. Commun. 53 (2017) 3010–3013. doi: 10.1039/C6CC09565H
33. [33]
  W. Xing, C. Tang, N. Wang, et al., Inorg. Chem. 59 (2020) 18452–18460. doi: 10.1021/acs.inorgchem.0c03176
34. [34]
  Z. Yang, Y. Yang, Y. Guo, et al., Chem. Mater. 31 (2019) 1110–1117. doi: 10.1109/apap47170.2019.9224671
35. [35]
  M.Y. Li, Z.J. Ma, B.X. Li, et al., Chem. Mater. 32 (2020) 4331–4339. doi: 10.1021/acs.chemmater.0c01258
36. [36]
  M. Yan, Z.D. Sun, W.D. Yao, et al., Inorg. Chem. Front. 7 (2020) 2451–2458. doi: 10.1039/d0qi00266f
37. [37]
  D. Mei, W. Cao, N. Wang, et al., Mater. Horiz. 8 (2021) 2330. doi: 10.1039/d1mh00562f
38. [38]
  W. Wang, D. Mei, S. Wen, et al., Chin. Chem. Lett. 33 (2022) 2301–2315. doi: 10.1016/j.cclet.2021.11.089
39. [39]
  H. Lin, L.J. Zhou, L. Chen, Chem. Mater. 24 (2012) 3406–3414. doi: 10.1021/cm301550a
40. [40]
  H. Lin, H. Chen, Y.J. Zheng, et al., Chem. Eur. J. 23 (2017) 10407–10412. doi: 10.1002/chem.201701679
41. [41]
  M.M. Chen, S.H. Zhou, W.B. Wei, et al., Adv. Optical Mater. 10 (2022) 2102123. doi: 10.1002/adom.202102123
42. [42]
  M.M. Chen, S.H. Zhou, W.B. Wei, et al., ACS Mater. Lett. 4 (2022) 1264–1269. doi: 10.1021/acsmaterialslett.2c00409
43. [43]
  H. Chen, M.Y. Ran, S.H. Zhou, et al., Chin. Chem. Lett. 34 (2023) 107838. doi: 10.1016/j.cclet.2022.107838
44. [44]
  Y. Chu, H.S. Wang, T.D. Abutukadi, et al., Small 20 (2024) 2305074.
45. [45]
  S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798–3813. doi: 10.1063/1.1656857
46. [46]
  M.Y. Ran, S.H. Zhou, W.B. Wei, et al., Small 19 (2023) 2300248. doi: 10.1002/smll.202300248
47. [47]
  H.D. Yang, M.Y. Ran, W.B. Wei, et al., Mater. Today Phys. 35 (2023) 101127. doi: 10.1016/j.mtphys.2023.101127
48. [48]
  M.Y. Ran, Z. Ma, H. Chen, et al., Chem. Mater. 32 (2020) 5890–5896. doi: 10.1021/acs.chemmater.0c02011
49. [49]
  J.X. Zhang, M.Y. Ran, X.T. Wu, et al., Inorg. Chem. Front. 10 (2023) 5244–5257. doi: 10.1039/d3qi01144e
50. [50]
  M.J. Zhang, X.M. Jiang, L.J. Zhou, et al., J. Mater. Chem. C 1 (2013) 4754–4760. doi: 10.1039/c3tc30808a
51. [51]
  M.Y. Li, B.X. Li, H. Lin, et al., Chem. Mater. 31 (2019) 6268–6275. doi: 10.1021/acs.chemmater.9b02389
52. [52]
  H. Chen, Y.Y. Li, B.X. Li, et al., Chem. Mater. 32 (2020) 8012–8019. doi: 10.1021/acs.chemmater.0c03008
53. [53]
  H.D. Yang, M.Y. Ran, S.H. Zhou, et al., Chem. Sci. 13 (2022) 10725–10733. doi: 10.1039/d2sc03760b
54. [54]
  Y.F. Shi, Z. Ma, B.X. Li, et al., Mater. Chem. Front. 6 (2022) 3054–3061. doi: 10.1039/d2qm00621a
55. [55]
  M.Y. Ran, S.H. Zhou, B.X. Li, et al., Chem. Mater. 34 (2022) 3853–3861. doi: 10.1021/acs.chemmater.2c00385
56. [56]
  S.N. Rashkeev, W.R.L. Lambrecht, B. Segall, Phys. Rev. B 57 (1998) 3905–3919.
57. [57]
  Z. Fang, J. Lin, R. Liu, et al., CrystEngComm 16 (2014) 10569–10580. doi: 10.1039/C4CE01606H
58. [58]
  K.J. Burke, Chem. Phys. 136 (2012) 150901.
59. [59]
  K. Govaerts, R. Saniz, B. Partoens, et al., Phys. Rev. B: Condens. Matter Mater. Phys. 87 (2013) 235210. doi: 10.1103/PhysRevB.87.235210
60. [60]
  D.A. Kleinman, Phys. Rev. 126 (1962) 1977. doi: 10.1103/PhysRev.126.1977
61. [61]
  M.M. Chen, Z. Ma, B.X. Li, et al., J. Mater. Chem. C 9 (2021) 1156. doi: 10.1039/d0tc05952h
62. [62]
  Y. Xiao, M.M. Chen, Y.Y. Shen, et al., Inorg. Chem. Front. 8 (2021) 2835. doi: 10.1039/d1qi00214g
63. [63]
  C. Liu, S.H. Zhou, Y. Xiao, et al., J. Mater. Chem. C 9 (2021) 15407. doi: 10.1039/d1tc04498b
64. [64]
  H. Lin, Y.Y. Li, M.Y. Li, et al., J. Mater. Chem. C 7 (2019) 4638–4643. doi: 10.1039/c9tc00647h
65. [65]
  C. Aversa, J.E. Sipe, Phys. Rev. B 52 (1995) 14636. doi: 10.1103/PhysRevB.52.14636
66. [66]
  S.N. Rashkeev, W.R.L. Lambrecht, B. Segall, Phys. Rev. B. 57 (1998) 3905.
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