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RESEARCH PAPER · Inorganic Chemistry · 2016

Midinfrared Nonlinear Optical Thiophosphates from LiZnPS4 to AgZnPS4: A Combined Experimental and Theoretical Study

Molin Zhou, Lei Kang, Jiyong Yao, Zheshuai Lin, Yicheng Wu, Chuangtian Chen

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Midinfrared Nonlinear Optical Thiophosphates from LiZnPS4 to AgZnPS4: A Combined Experimental and Theoretical StudyOriginalNa 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302Single-step sub-200 fs mid-infrared generation from an optical parametric oscillator synchronously pumped by an erbium fiber laser13Analysis and prediction of mid-IR nonlinear optical metal sulfides with diamond-like structures335Phase Transition and Second Harmonic Generation in Thiophosphates Ag2Cd(P2S6) and AgCd3(PS4)S2 Containing Two Second-Order Jahn–Teller Distorted Cations47Recent achievements on middle and far-infrared second-order nonlinear optical materials433Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses77Screening novel candidates for mid-IR nonlinear optical materials from I 3 –V–VI 4 compounds51Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Thiophosphates Containing Ag+ and Lone-Pair Cations with Interchiral Double Helix Show Both Ionic Conductivity and Phase Transition19First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides12Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Na2ZnSn2S6: A mixed-metal thiostannate with large second-harmonic generation response activated by penta-tetrahedral [ZnSn4S14]10− clusters10New Compressed Chalcopyrite-like Li2BaMIVQ4 (MIV = Ge, Sn; Q = S, Se): Promising Infrared Nonlinear Optical Materials245First principle study of nonlinear optical crystals15Structural insights into T 2 -cluster-containing chalcogenides with vertex-, edge- and face-sharing connection modes of NaQ 6 ligands: Na 3 ZnM III Q 4 (M III = In, Ga; Q = S, Se)13Correlation of Structure and Fast Ion Conductivity in the Solid Solution Series Li1+2xZn1–xPS456LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials88Prediction and Characterization of NaGaS2, A High Thermal Conductivity Mid-Infrared Nonlinear Optical Material for High-Power Laser Frequency Conversion38Zn 3 P 2 S 8 : A Promising Infrared Nonlinear-Optical Material with Excellent Overall Properties69Cyano-Based Materials with Giant Optical Anisotropy and Second Harmonic-Generation Effect24Experimental study on nonlinear−optical property of Ag4P2Se66Recent progress on new infrared nonlinear optical materials with application prospect133Adjustable optical nonlinearity in d 10 cations containing chalcogenides via dp hybridization interaction13Ag 7 TaSe 6 : a new noncentrosymmetric selenide with fascinating “three in one” coordination modes and a strong second harmonic generation response13Lone pair effects on ternary infrared nonlinear optical materials19[Ge2S5(S2)]4−, A NLO‐Active Unit Leading to an Asymmetric Structure Discovered in Li2Cs4Ge2S5(S2)Cl2: An Experimental and Theoretical study18First-Principles Design and Simulations Promote the Development of Nonlinear Optical Crystals299Enhanced optical anisotropy via dimensional control in alkali-metal chalcogenides18Li 2 CdSiS 4 , a promising IR NLO material with a balanced E g and SHG response originating from the effect of Cd with d 10 configuration36Mixed-metal thiophosphate CuCd 3 PS 6 : an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture33Molecular Construction from AgGaS 2 to CuZnPS 4 : Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement96HgCuPS4: An Exceptional Infrared Nonlinear Optical Material with Defect Diamond-like Structure145Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials130Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response67A series of M 3 PS 4 (M = Ag, Cu and Ag/Cu) thiophosphates with diamond-like structures exhibiting large second harmonic generation responses and moderate ion conductivities28La 6 Cd 0.75 Ga 2 Q 11.5 Cl 2.5 (Q = S and Se): two new nonlinear optical chalcohalides with a large laser-induced damage threshold15New nonlinear optical-active AAgGa 6 S 10 (A = K, Rb, Cs) featuring {[AgGa 6 S 10 ] − } ∞ framework and high laser damage threshold42Structural Modulation from Cu 3 PS 4 to Cu 5 Zn 0.5 P 2 S 8 : Single-Site Aliovalent-Substitution-Driven Second-Harmonic-Generation Enhancement28A review of the structural diversity of [P x S y ] n − motifs and their potential application prospects in metal thiophosphates21Highly Distorted [HgS 4 ] Motif-Driven Structural Symmetry Degradation and Strengthened Second-Harmonic Generation Response in the Defect Diamond-Like Chalcogenide Hg 3 P 2 S 846Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units49Investigation into Structural Variation from 3D to 1D and Strong Second Harmonic Generation of the AHgPS4 (A+ = Na+, K+, Rb+, Cs+) Family26Highly polarized [GeOTe 3 ] motif-driven structural order promotion and an enhanced second harmonic generation response in the new nonlinear optical oxytelluride Ba 3 Ge 2 O 4 Te 334Pnictides: An emerging class of infrared nonlinear optical material candidates47Building-block approach to the discovery of Na8Mn2(Ge2Se6)2: A polar chalcogenide exhibiting promising harmonic generation signals with a high laser-induced damage threshold9AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances21Alkali metal partial substitution-induced improved second-harmonic generation and enhanced laser-induced damage threshold for Ag-based sulfides21Infrared nonlinear optical sulfide CsCd 4 In 5 S 12 exhibiting large second harmonic generation response16KAg3Ga8S14: An Mid- and Far-infrared Nonlinear Optical Material Exhibiting High Laser-induced Damage Threshold※3LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence16Wide band gap thiophosphates ASrPS 4 (A = Li, Na, K, Rb, Cs): cation size effect induced successive structural transformation13Two Nonlinear Optical Thiophosphates Cu 5 Hg 0.5 P 2 S 8 and AgHg 3 PS 6 Activated by Their Tetrahedra-Stacking Architecture12Synthesis, crystal structure, optical bandgap, and electronic structure of Cs2FeP2S62SrAgAsS4: A Noncentrosymmetric Sulfide with Good Infrared Nonlinear Optical Performance Induced by Aliovalent Substitution from Centrosymmetric SrGa2S412Eu 2 P 2 S 6 : The First Rare‐Earth Chalcogenophosphate Exhibiting Large Second‐Harmonic Generation Response and High Laser‐Induced Damage Threshold143Eu2P2S6: The First Rare‐Earth Chalcogenophosphate Exhibiting Large Second‐Harmonic Generation Response and High Laser‐Induced Damage Threshold7Hg2P2S6: A layered mercury hexathiodiphosphate (IV) with large birefringence11(Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold14Novel structural transformation in K3ReP2S8 thiophosphates originating from the rare-earth (Re) cation sizes induced local coordination asymmetry25Synthesis, Crystal and Electronic Structures, Nonlinear Optical Properties, and Magnetic Properties of Two Thiophosphates: KInP2S7 and KCrP2S79Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90AgIn 5 Se 8 : a defect diamond-like non-linear optical selenide21From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement7LaAeAl 3 S 7 (Ae = Ca, Sr): Cairo pentagonal layered thioaluminates achieving a good balance between a strong second harmonic generation response and a wide bandgap23Na 6 Sn 3 P 4 S 16 : Sn( ii )-chelated PS 4 groups inspired an ultra-strong SHG response22Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26Revisiting two thiophosphate compounds constituting d 0 transition metal HfP 2 S 6 and d 10 transition metal α-Ag 4 P 2 S 6 as multifunctional materials for combining second harmonic generation response and photocurrent response12Phase Competition and Strong SHG Responses of the Li2MIIMIVSe4 Family: Atom Response Theory Predictions versus Experimental Results24Zn2BS3Br: An Infrared Nonlinear Optical Material with Significant Dual-Property Enhancements Designed through a Template Grafting Strategy20The induced polarization enhanced birefringence in AlPS4 family: A first-principles investigation6Defect diamond-like tellurides as infrared nonlinear optical materials with giant second-harmonic generation tensor13AEAg7(PS4)3 (AE = Ba, Sr): The homovalent substitution of lead by alkaline earth metals achieves the separation of the two phases and enlarges the band gap1The compatibly large nonlinear optical effect and high laser-induced damage threshold in a thiophosphate CsInP2S7 constructed with [P2S7]4- and [InS6]9-15Na 6 Mg 3 P 4 S 16 and RbMg 2 PS 4 Cl 2 : two Mg-based thiophosphates with ultrawide bandgaps resulting from [MgS 6 ] and [MgS x Cl 6− x ] octahedra4Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Reconstructing nearly isotropic microstructures to construct a one-dimensional framework causing record birefringence in thiophosphates13Infrared nonlinear optical materials with multiple strongly ionic cations5Vacancy‐Induced Extraordinary Second Harmonic Generation Response for Diamond‐Like Cu3PS49Influence of Cation-Size Effects of Alkaline Earth (Ae) Metals on Dimensionality and Optical Anisotropy Regulation in K4AeP2S8 Thiophosphates5Structure‐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 Response28A Congruent-Melt Infrared Nonlinear Optical Crystal Na4SrAs2S83Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17Partial congener substitution induced wide band gap witnessed in diamond-like chalcogenide ZnHg 2 P 2 S 8 and its second-order nonlinear optical properties3Chalcophosphates: A plentiful source of infrared nonlinear optical materials42Reinforced Nonlinear Optical Performances Induced by P‐P Homoatomic Bond in Phosphide SrIn 3 Si 4 P 1131Reinforced Nonlinear Optical Performances Induced by P‐P Homoatomic Bond in Phosphide SrIn 3 Si 4 P 116The Influence of Different Group Distortions on the Structure–Property Relationship of Alkali Metal Thiophosphate0Vacancy-driven tetrahedral distortion leading to exceptional second harmonic generation3ABCQ4型硫属化物红外非线性光学材料的构效关系（特邀）0Optimal three-dimensional [Ag 4 P 2 S 6 ]-framework assembly directed by a threefold roto-inversion axis for enhanced birefringence0高性能硫属化物红外非线性光学材料构效关系（特邀）0Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals13Mid‐ to Far‐Infrared Nonlinear Optical Crystals: Design Strategies, Structure–Property Relationships and Engineering Prospects0AVP2S7 (A = K, Rb): Dual-Optimized Infrared Nonlinear Optical Thiophosphates via Heterovalent-Substitution-Driven Symmetry Breaking and Reinforced Interlayer Interactions0NaGa2PS6: A Noncentrosymmetric Thiophosphate with Wide Band Gap and High Laser-Induced Damage Threshold0

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  1. Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold

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  2. Single-step sub-200 fs mid-infrared generation from an optical parametric oscillator synchronously pumped by an erbium fiber laser

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  3. Analysis and prediction of mid-IR nonlinear optical metal sulfides with diamond-like structures

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  4. Phase Transition and Second Harmonic Generation in Thiophosphates Ag2Cd(P2S6) and AgCd3(PS4)S2 Containing Two Second-Order Jahn–Teller Distorted Cations

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  5. Recent achievements on middle and far-infrared second-order nonlinear optical materials

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  6. Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses

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  7. Screening novel candidates for mid-IR nonlinear optical materials from I 3 –V–VI 4 compounds

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  8. Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 6

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  9. Thiophosphates Containing Ag+ and Lone-Pair Cations with Interchiral Double Helix Show Both Ionic Conductivity and Phase Transition

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  10. First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides

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  11. Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship

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  12. Na2ZnSn2S6: A mixed-metal thiostannate with large second-harmonic generation response activated by penta-tetrahedral [ZnSn4S14]10− clusters

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  13. New Compressed Chalcopyrite-like Li2BaMIVQ4 (MIV = Ge, Sn; Q = S, Se): Promising Infrared Nonlinear Optical Materials

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  14. First principle study of nonlinear optical crystals

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  15. Structural insights into T 2 -cluster-containing chalcogenides with vertex-, edge- and face-sharing connection modes of NaQ 6 ligands: Na 3 ZnM III Q 4 (M III = In, Ga; Q = S, Se)

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  16. Correlation of Structure and Fast Ion Conductivity in the Solid Solution Series Li1+2xZn1–xPS4

    Chemistry of Materials · 2018-01-23

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  17. LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials

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  18. Prediction and Characterization of NaGaS2, A High Thermal Conductivity Mid-Infrared Nonlinear Optical Material for High-Power Laser Frequency Conversion

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  19. Zn 3 P 2 S 8 : A Promising Infrared Nonlinear-Optical Material with Excellent Overall Properties

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  20. Cyano-Based Materials with Giant Optical Anisotropy and Second Harmonic-Generation Effect

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  21. Experimental study on nonlinear−optical property of Ag4P2Se6

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  22. Recent progress on new infrared nonlinear optical materials with application prospect

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  23. Adjustable optical nonlinearity in d 10 cations containing chalcogenides via dp hybridization interaction

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  24. Ag 7 TaSe 6 : a new noncentrosymmetric selenide with fascinating “three in one” coordination modes and a strong second harmonic generation response

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  25. Lone pair effects on ternary infrared nonlinear optical materials

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  26. [Ge2S5(S2)]4−, A NLO‐Active Unit Leading to an Asymmetric Structure Discovered in Li2Cs4Ge2S5(S2)Cl2: An Experimental and Theoretical study

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  31. Molecular Construction from AgGaS 2 to CuZnPS 4 : Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement

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  32. HgCuPS4: An Exceptional Infrared Nonlinear Optical Material with Defect Diamond-like Structure

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  33. Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials

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  34. Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials

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  35. From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response

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  36. A series of M 3 PS 4 (M = Ag, Cu and Ag/Cu) thiophosphates with diamond-like structures exhibiting large second harmonic generation responses and moderate ion conductivities

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  37. La 6 Cd 0.75 Ga 2 Q 11.5 Cl 2.5 (Q = S and Se): two new nonlinear optical chalcohalides with a large laser-induced damage threshold

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  38. New nonlinear optical-active AAgGa 6 S 10 (A = K, Rb, Cs) featuring {[AgGa 6 S 10 ] − } ∞ framework and high laser damage threshold

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  39. Structural Modulation from Cu 3 PS 4 to Cu 5 Zn 0.5 P 2 S 8 : Single-Site Aliovalent-Substitution-Driven Second-Harmonic-Generation Enhancement

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  40. A review of the structural diversity of [P x S y ] n − motifs and their potential application prospects in metal thiophosphates

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  41. Highly Distorted [HgS 4 ] Motif-Driven Structural Symmetry Degradation and Strengthened Second-Harmonic Generation Response in the Defect Diamond-Like Chalcogenide Hg 3 P 2 S 8

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  42. Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials

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  43. SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units

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  44. Investigation into Structural Variation from 3D to 1D and Strong Second Harmonic Generation of the AHgPS4 (A+ = Na+, K+, Rb+, Cs+) Family

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  45. Highly polarized [GeOTe 3 ] motif-driven structural order promotion and an enhanced second harmonic generation response in the new nonlinear optical oxytelluride Ba 3 Ge 2 O 4 Te 3

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  46. Pnictides: An emerging class of infrared nonlinear optical material candidates

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  47. Building-block approach to the discovery of Na8Mn2(Ge2Se6)2: A polar chalcogenide exhibiting promising harmonic generation signals with a high laser-induced damage threshold

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  48. AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances

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  49. Alkali metal partial substitution-induced improved second-harmonic generation and enhanced laser-induced damage threshold for Ag-based sulfides

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    Wenfeng Zhou, Ming Geng, Mei Yan, Nian‐Tzu Suen, Wenlong Liu, Sheng‐Ping Guo

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  50. Infrared nonlinear optical sulfide CsCd 4 In 5 S 12 exhibiting large second harmonic generation response

    Journal of Materials Chemistry C · 2022-01-01

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