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RESEARCH PAPER · Small · 2023

Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response

Yu Chu, Hongshan Wang, Tudi Abutukadi, Zhi Li, Miriding Mutailipu, Xin Su, Zhihua Yang, Junjie Li, Shilie Pan

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Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation ResponseOriginalA new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response34Ba 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units8From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency21MB 3 P 2 S 10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B 6 P 4 S 20 ] T3-supertetrahedra2Synthesis of chiral high-entropy sulfides for non-linear optical applications13Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers5Double alkaline earth metals sulfide SrMgGeS4 with high laser-induced damage threshold and strong second-harmonic generation29Theoretical investigations on ternary defective diamond-like infrared nonlinear optical materials in Be-Ga-Se system18[RbSr 3 X][(BS 3 ) 2 ] (X = Cl, Br): two salt-inclusion thioborates with large birefringence and structure transformation from centrosymmetric to asymmetric8NaREP 2 Se 6 (RE = Y, Sm, Gd–Dy): Quaternary Rare-Earth Selenophosphates with Unique 3D {[REP 2 Se 6 ] − } ∞ Framework Built by RESe 8 and P 2 Se 6 Motifs and Multiple Properties4Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy10Nonlinear Optical Phosphide CuInSi2P4: The Inaugural Member of Diamond-Like Family I–III–IV2–V4 Inspired by ZnGeP216“Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect80Ba 2 GeF 2 Q 3 (Q = S, Se) and Ba 3 GeF 2 Se 4 : new F-based chalcohalides with enhanced birefringence9Chemical modulation of A I RE III C IV QVI4 family compounds for band gap and optical anisotropy enhancement16Hg 3 AsS 4 X (X = Cl and Br): two Hg-based chalcogenides as long-wave infrared nonlinear optical crystals with superior comprehensive performances33New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15Pb 3.5 GeS 4 Br 3 : the first phase-matching thiogermanate halide infrared nonlinear optical material12Pb 6 Ba 3 Si 2 S 8 I 10 : a new thiohalide with a quasi-two-dimensional structure and wide band gap2Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence10Salt-inclusion sulfides [K 4 Cl][M II 11 In 9 S 26 ] (M II = Zn, Cd) displaying robust nonlinear optical activity4Syntheses, crystal structures and photocurrent responses of Cs 2 Ag 2 Sb 2 S 5 and CsAgSb 4 S 7 with thiourea as a mineralizer4Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds31β -CsHg 2 I 5 , a compound with rare [Hg 2 I 5 ] dimers and large optical anisotropy2Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups9Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction26KREP 2 S 6 (RE = Sm, Gd, Tb, Dy): A Series of Polar Rare-Earth Thiophosphates with High Laser-Induced Damage Thresholds and Moderate Nonlinear-Optical Responses Synergistically Contributed by Isolated P 2 S 6 Units and {[RE 2 S 15 ] 24– } ∞ Layers8The first Hg-based oxychalcogenide Sr2HgGe2OS6: Achieving balanced IR nonlinear optical properties through synergistic cation and anion substitution28Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials24Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials1Ag 2 GeS 3 : A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response28(C5H12N2S)Hg(NO3)2: A Mercury Nitrate Nonlinear Optical Crystal Motivated by Heteroatom Coordination Strategy9Computer‐Aided Development of New Nonlinear Optical Materials38Computer‐Aided Development of New Nonlinear Optical Materials14Hg4InS2Cl5: Achieving Giant Optical Anisotropy by Introducing Well‐Aligned Linear [Hg2S2] Units14Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective109A wide band gap selenohalide Cs 9 Si 8 Se 20 Cl with unprecedented [CsSe 7 Cl] mixed anionic units2Cd 5 Te 4 O 12 X 2 (X = Cl, Br, I): a new oxyhalide family with [CdO 4 X] mixed anionic units and adjustable optical properties4Designing infrared nonlinear optical crystals, Sr 2 MgSn 2 OS 6 and Sr 2 SnGa 2 OS 6 , with hybrid anionic frameworks via a double substitution strategy4First-principles study of mechanism of high birefringence in alkali metal vanadates AV3O8 (A = Li, Na, K, Rb)0Mesoporous materials 2.0: innovations in metals and chalcogenides for future applications28Partial congener substitution induced wide band gap witnessed in diamond-like chalcogenide ZnHg 2 P 2 S 8 and its second-order nonlinear optical properties3Prismatic crystal field stabilized divalent rare-earth chalcogenide REIIBII6CIII6QVI16 with bifunctionality30Structural diversity and photocurrent responses of multi-component chalcogenidometalates8新型非线性光学晶体和双折射晶体的研究进展（特邀）4Pb9Si8O22Cl6 and Pb3.07Ca1.93Si3O11: Two Ultraviolet Nonlinear Optical Materials Exhibit a Moderate Second Harmonic Generation Response1Sr2Zn(C3N3O3)2: An Alkaline Earth and d10 Transition Metal Based Ultraviolet Cyanurate with Large Birefringence6A new selenide semiconductor NaMn3Ga3Se8 with strong second-harmonic generation and significant luminescence property5Synergically Assembling Advantageous Groups toward High‐Performance Infrared Nonlinear Optical Materials A II CdSiSe 4 (A II = Sr, Ba)40[K2PbI][Ga7Se12]: A New Lead-Containing Nonlinear Optical Material with Moderate Second-Harmonic Generation Response and Large Birefringence5Planar [HgCl 3 ] and V‑Shaped [HgCl 2 ] Units Synergistically Creating a Prominent Halide Birefringent Crystal β ‐CsHg 2 Cl 5 with Wide‐Spectrum7The Influence of Different Group Distortions on the Structure–Property Relationship of Alkali Metal Thiophosphate0Cd 7 I 12 Q·As 4 Q n (Q = S, Se; n = 3, 4): In Situ Alteration of Functional Molecules in Polar Metal Inorganic Framework Tailoring High‐Performance Infrared Nonlinear Optical Crystals9Large Nonlinear Optical Response and Slowed Electron‐Phonon Scattering in a Kagome‐type Flat Band Semiconductor0Introduction of Diverse Divalent Main-Group Metal Cations to Tune the Physical Properties of Rare-Earth Thiophosphates7Vacancy-driven tetrahedral distortion leading to exceptional second harmonic generation3[HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap12NaAg3Ga8S14: A new diamond-like framework infrared nonlinear optical material derived from AgGaS26BaAl2MS6 (M = Si and Ge): the rational construction of diamond-like structures with ultrawide band gap by group-optimization approach6Reactive flux assisted metal oxide–boron–sulfur routine for syntheses of CsRESiS 4 (RE = Sm, Gd–Ho): featuring nonlinear optical activity and wide band gaps5Broadband infrared-transparent crystals enabled by heterologous isomorphic substitution0Centrosymmetric to noncentrosymmetric structure transition of the RbREP 2 Se 6 (RE = La–Nd, Sm, Ho–Yb) series: crystal growth, magnetic and optical properties4Inorganic Ge-based ferroelectric perovskites towards quasi-phase-matching in the infrared region0Anion-Centered Engineering for Simultaneously Enhancing Birefringence and Band Gap in Chalcogenides1Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals13Topology-Guided Discovery of BaIn 2 Si 7 P 12 : A Quaternary Diamond-like Framework Phosphide with Giant Second-Harmonic Generation and High Laser-Induced Damage Threshold22Recent Progress in Hg-Based Oxysalt Crystals for Nonlinear Optics and Birefringence Applications5Defect Diamond‐Like d 10 Metal Indium Selenium With Strong Second‐Harmonic Generation and Enhanced Laser‐Induced Damage Threshold2Linear [ICl 2 ] Units Induced Giant Optical Anisotropy in AICl 2 (A = NH 4 , Rb): A Pathway to Advanced Birefringent Materials4Regulating B‐O Arrangement Boosts Anisotropy in a Simple Rubidium Borate, Leading to a High‐Performance UV NLO Crystal0Mid‐ to Far‐Infrared Nonlinear Optical Crystals: Design Strategies, Structure–Property Relationships and Engineering Prospects0Cation-substitution-driven electronic, nonlinear optical, elastic, and thermal transport properties of layered AeHgGeSe4 (Ae = Ba, Sr): A first-principles study0AgEuPS4: Unlocking the Centrosymmetric Shackle of Rare-Earth Thiophosphates via Microscopic Distortion Cascading for Enhanced Second-Harmonic Generation Response0Laporte Selection Rule Induced the Suppression of d ‐ d Transitions and Vacancies Enhanced the Second Harmonic Generation in I 4¯‐MnGa 2 S 40AlGaS3: a wide band gap ternary diamond-like infrared nonlinear optical material with high laser-induced damage threshold1

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  1. A new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response

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  2. Ba 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units

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    Jiazheng Zhou, Linan Wang, Hongshan Wang, Ling Luo, Junjie Li, Feng Yu

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  3. From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency

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    Pengfei Li, Chun‐Li Hu, Bing-Xuan Li, Jiang‐Gao Mao, Fang Kong

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  4. MB 3 P 2 S 10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B 6 P 4 S 20 ] T3-supertetrahedra

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    Jiazheng Zhou, Xin Su, Ling Luo, Junjie Li, Feng Yu

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  5. Synthesis of chiral high-entropy sulfides for non-linear optical applications

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  6. Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers

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  7. Double alkaline earth metals sulfide SrMgGeS4 with high laser-induced damage threshold and strong second-harmonic generation

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  8. Theoretical investigations on ternary defective diamond-like infrared nonlinear optical materials in Be-Ga-Se system

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  9. [RbSr 3 X][(BS 3 ) 2 ] (X = Cl, Br): two salt-inclusion thioborates with large birefringence and structure transformation from centrosymmetric to asymmetric

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    Yihan Yun, Xueling Hou, Zhihua Yang, Guangmao Li, Shilie Pan

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  10. NaREP 2 Se 6 (RE = Y, Sm, Gd–Dy): Quaternary Rare-Earth Selenophosphates with Unique 3D {[REP 2 Se 6 ] − } ∞ Framework Built by RESe 8 and P 2 Se 6 Motifs and Multiple Properties

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    Chen‐Yi Zhao, Zi‐Xia Chen, Wen‐Dong Yao, Wenfeng Zhou, Wenlong Liu, Sheng‐Ping Guo

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  11. Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy

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    Chenyao Zhao, Dazhi Lu, Xinyu Tian, Jingjing Xu, Bingbing Zhang, Kui Wu, Haohai Yu, Huaijin Zhang

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  12. Nonlinear Optical Phosphide CuInSi2P4: The Inaugural Member of Diamond-Like Family I–III–IV2–V4 Inspired by ZnGeP2

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    Ming‐Shu Zhang, Bin‐Wen Liu, Xiao‐Ming Jiang, Guo‐Cong Guo

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  13. “Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect

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  14. Ba 2 GeF 2 Q 3 (Q = S, Se) and Ba 3 GeF 2 Se 4 : new F-based chalcohalides with enhanced birefringence

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    Kaixuan Li, Hongping Wu, Hongwei Yu, Zhanggui Hu, Jiyang Wang, Yicheng Wu

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  15. Chemical modulation of A I RE III C IV QVI4 family compounds for band gap and optical anisotropy enhancement

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  16. Hg 3 AsS 4 X (X = Cl and Br): two Hg-based chalcogenides as long-wave infrared nonlinear optical crystals with superior comprehensive performances

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  17. New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution

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  18. Pb 3.5 GeS 4 Br 3 : the first phase-matching thiogermanate halide infrared nonlinear optical material

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  19. Pb 6 Ba 3 Si 2 S 8 I 10 : a new thiohalide with a quasi-two-dimensional structure and wide band gap

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  20. Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence

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  21. Salt-inclusion sulfides [K 4 Cl][M II 11 In 9 S 26 ] (M II = Zn, Cd) displaying robust nonlinear optical activity

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  22. Syntheses, crystal structures and photocurrent responses of Cs 2 Ag 2 Sb 2 S 5 and CsAgSb 4 S 7 with thiourea as a mineralizer

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  23. Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds

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  24. β -CsHg 2 I 5 , a compound with rare [Hg 2 I 5 ] dimers and large optical anisotropy

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  25. Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups

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  26. Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction

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  28. The first Hg-based oxychalcogenide Sr2HgGe2OS6: Achieving balanced IR nonlinear optical properties through synergistic cation and anion substitution

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  29. Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

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  31. Ag 2 GeS 3 : A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response

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  32. (C5H12N2S)Hg(NO3)2: A Mercury Nitrate Nonlinear Optical Crystal Motivated by Heteroatom Coordination Strategy

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  33. Computer‐Aided Development of New Nonlinear Optical Materials

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  35. Hg4InS2Cl5: Achieving Giant Optical Anisotropy by Introducing Well‐Aligned Linear [Hg2S2] Units

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  42. Partial congener substitution induced wide band gap witnessed in diamond-like chalcogenide ZnHg 2 P 2 S 8 and its second-order nonlinear optical properties

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