Citation: 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[J]. Chinese Chemical Letters, ;2026, 37(10): 111639. doi: 10.1016/j.cclet.2025.111639 shu

Bromine for iodine: Unlocking short-wavelength UV phase matching in nonlinear optical metal halides

Ming-Chang Wang ^{a, 1} ,
Zhi Lin ^{a, 1} ,
Jia-Jia Li ^a ,
Jia-Min Lian ^a ,
Yun-Xia Hu ^a ,
Yan Chen ^{b, c, *,} ,
Ke-Zhao Du ^{a, b, *,} ,
Jin Chen ^{a, b, *,}

a.
Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Collage of Chemistry and Material Science, Fujian Normal University, Fuzhou 350007, China
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c.
School of Environmental and Material Engineering, Yantai University, Yantai 264005, China

yanchen@ytu.edu.cn

duke@fjnu.edu.cn

cj2015@fjnu.edu.cn

Received Date: 3 June 2025
Revised Date: 14 July 2025
Accepted Date: 25 July 2025
Available Online: 27 July 2025

Figures(3)

The development of high-performance nonlinear optical (NLO) crystals for the short-wave ultraviolet (UV) region remains a significant challenge. In this work, four novel organic-inorganic metal halides, (3-QUO)₂MX₄ (3-QUO = 1-azabicyclo[2.2.2]octan-3-one; M = Zn, Cd; X = Br, I), were developed. Our initial efforts with the iodide compounds, (3-QUO)₂ZnI₄ and (3-QUO)₂CdI₄, yielded materials with modest second-harmonic generation (SHG) responses and, critically, they were non-phase-matchable. To overcome this, we employed a halogen-substitution strategy, replacing iodine with bromine, guided by the principle of bandgap widening. This approach successfully yielded (3-QUO)₂ZnBr₄ and (3-QUO)₂CdBr₄, which exhibit superior short-wave UV transparency and achieve phase-matchable SHG. Specifically, (3-QUO)₂ZnBr₄ shows a wide bandgap of 5.10 eV (UV cutoff: 220 nm) and a phase-matchable SHG response of 1.5 times that of KH₂PO₄ (KDP). Similarly, (3-QUO)₂CdBr₄ possesses a bandgap of 4.55 eV (UV cutoff: 245 nm) and an SHG response of 1.8 × KDP. Furthermore, these materials exhibit yellowish-white fluorescence under blue light excitation. This work demonstrates an effective approach to simultaneously tune bandgap, SHG response, and phase-matching capabilities for short-wave UV NLO applications.
- OIMHs,
- Large SHG response,
- Wide bandgap,
- Halogen substitution,
- Short-wave UV phase matching
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