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
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