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RESEARCH PAPER · Chemistry of Materials · 2014

Li2CdGeS4, A Diamond-Like Semiconductor with Strong Second-Order Optical Nonlinearity in the Infrared and Exceptional Laser Damage Threshold

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Li2CdGeS4, A Diamond-Like Semiconductor with Strong Second-Order Optical Nonlinearity in the Infrared and Exceptional Laser Damage ThresholdOriginalOptical Nonlinearity in Cu2CdSnS4 and α/β-Cu2ZnSiS4: Diamond-like Semiconductors with High Laser-Damage Thresholds87ChemInform Abstract: Li2CdGeS4, a Diamond‐Like Semiconductor with Strong Second‐Order Optical Nonlinearity in the Infrared and Exceptional Laser Damage Threshold.0Highly efficient infrared optical nonlinearity of a wide-bandgap chalcogenide Li_2CdGeS_422Syntheses and characterization of one-dimensional alkali metal antimony(III) thiostannates(IV), A2Sb2Sn3S10 (A=K, Rb, Cs)21Field-Induced Spin-Flop in Antiferromagnetic Semiconductors with Commensurate and Incommensurate Magnetic Structures: Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS)28Syntheses, Structures, and Nonlinear-Optical Properties of Metal Sulfides Ba2Ga8MS16 (M = Si, Ge)94Infrared nonlinear optical properties of lithium-containing diamond-like semiconductors Li 2 ZnGeSe 4 and Li 2 ZnSnSe 457SnGa 2 GeS 6 : synthesis, structure, linear and nonlinear optical properties46Second Harmonic Generation Response Optimized at Various Optical Wavelength Ranges through a Series of Cubic Chalcogenides Ba6Ag2.67+4δSn4.33−δS16–xSex41Phase-Change Behavior and Nonlinear Optical Second and Third Harmonic Generation of the One-Dimensional K(1–x)CsxPSe6 and Metastable β-CsPSe662Outstanding Laser Damage Threshold in Li2MnGeS4 and Tunable Optical Nonlinearity in Diamond-Like Semiconductors120Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE3Sb0.33SiS7 (RE=La, Pr)24Analysis of chemical ordering and fragility for Ge–Se–In glasses45A new class of lithium ion conductors with tunable structures and compositions: Quaternary diamond-like thiogermanates14Polymorphism and second harmonic generation in a novel diamond-like semiconductor: Li2MnSnS434RbMgCO3F: A New Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material341Li 3 AlSiO 5 : the first aluminosilicate as a potential deep-ultraviolet nonlinear optical crystal with the quaternary diamond-like structure54[A 3 X][Ga 3 PS 8 ] (A = K, Rb; X = Cl, Br): promising IR non-linear optical materials exhibiting concurrently strong second-harmonic generation and high laser induced damage thresholds189BaCdSnS 4 and Ba 3 CdSn 2 S 8 : syntheses, structures, and non-linear optical and photoluminescence properties97Microscopic interactions governing phase matchability in nonlinear optical materials6Pb 5 Ga 6 ZnS 15 : a noncentrosymmetric framework with chains of T2-supertetrahedra41Syntheses, structures, physical and electronic properties of quaternary semiconductors: Cs[RE 9 Cd 4 Se 18 ] (RE = Tb–Tm)14Revealing the origin of the strong second harmonic generation of Li2CdXS4 and Li2CdXS4 (X = Ge or Sn)8The structure and band gap design of high Si doping level Ag1−xGa1−xSixSe2 (x=1/2)15Lead nitrate hydroxide: A strong second-order optical nonlinearity acentric crystal with high laser damage thresholds13Syntheses and structural characterization of non-centrosymmetric Na2M2M'S6 (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides36Syntheses, structural variants and characterization of AInM′S4 (A=alkali metals, Tl; M′ = Ge, Sn) compounds; facile ion-exchange reactions of layered NaInSnS4 and KInSnS4 compounds40Na 2 Hg 3 M 2 S 8 (M = Si, Ge, and Sn): New Infrared Nonlinear Optical Materials with Strong Second Harmonic Generation Effects and High Laser-Damage Thresholds186Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302Exploring the electronic structure of Pb2+ ions containing material Pb16(OH)16(NO3)162A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS725Investigation of electronic structure and thermodynamic properties of quaternary Li-containing chalcogenide diamond-like semiconductors2The role of the alkali and chalcogen atoms on the stability of the layered chalcogenide A 2 M I I M 3 I V Q 8 (A = alkali-metal; M = metal-cations; Q = chalcogen) compounds: a density functional theory investigation within van der Waals corrections8Analysis and prediction of mid-IR nonlinear optical metal sulfides with diamond-like structures336Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Mixed-Metal Carbonate Fluorides as Deep-Ultraviolet Nonlinear Optical Materials259Recent achievements on middle and far-infrared second-order nonlinear optical materials433Ba 6 Li 2 CdSn 4 S 16 : lithium substitution simultaneously enhances band gap and SHG intensity44BaCu 2 M IV Q 4 (M IV = Si, Ge, and Sn; Q = S, Se): synthesis, crystal structures, optical performances and theoretical calculations54Li 2 CdGeSe 4 and Li 2 CdSnSe 4 : biaxial nonlinear optical materials with strong infrared second-order responses and laser-induced damage thresholds influenced by photoluminescence54Lithium borate Li 3 B 5 O 8 (OH) 2 with large second harmonic generation and a high damage threshold in the deep-ultraviolet spectral range16Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses78Na 6 Si 3 S 8 O: the first example of a sulfide silicate exhibiting unusual tri-polymerized [Si 3 S 8 O] 6− units without S–O bonds8The first quaternary diamond-like semiconductor with 10-membered LiS 4 rings exhibiting excellent nonlinear optical performances104The influence of oxygen vacancies on the linear and nonlinear optical properties of Pb 7 O(OH) 3 (CO 3 ) 3 (BO 3 )41Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Two haloid borate crystals with large nonlinear optical response32Wide band gap design of new chalcogenide compounds: KSrPS 4 and CsBaAsS 422Superpolyhedron-Built Second Harmonic Generation Materials Exhibit Large Mid-Infrared Conversion Efficiencies and High Laser-Induced Damage Thresholds101Second harmonic generation response of the cubic chalcogenides Ba(6−x)Srx[Ag(4−y)Sn(y/4)](SnS4)49Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion64Spin-polarized Second Harmonic Generation from the Antiferromagnetic CaCoSO Single Crystal148Na2ZnSn2S6: A mixed-metal thiostannate with large second-harmonic generation response activated by penta-tetrahedral [ZnSn4S14]10− clusters10Ba 6 Zn 7 Ga 2 S 16 : A Wide Band Gap Sulfide with Phase-Matchable Infrared NLO Properties111Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4Ga5S12 (A=K, Rb, Cs) with 3D Diamond‐like Frameworks65Pb0.65Mn2.85Ga3S8 and Pb0.72Mn2.84Ga2.95Se8: Two Quaternary Metal Chalcognides with Open-Tunnel-Framework Structures Displaying Intense Second Harmonic Generation Responses and Interesting Magnetic Properties17Panoramic Synthesis as an Effective Materials Discovery Tool: The System Cs/Sn/P/Se as a Test Case46Room‐Temperature Synthesis of Three Compounds Featuring the [Ge4S10]4– Anion from a Water‐Soluble Thiogermanate Precursor7Novel ternary semiconductor CdLa2X4 (X=S or Se) single crystal with efficient second harmonic generation in the visible spectral range11New Compressed Chalcopyrite-like Li2BaMIVQ4 (MIV = Ge, Sn; Q = S, Se): Promising Infrared Nonlinear Optical Materials245Selective enhancement of optical nonlinearity in two-dimensional organic-inorganic lead iodide perovskites193Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)49Li2MnSnSe4: A New Quaternary Diamond‐Like Semiconductor with Nonlinear Optical Response and Antiferromagnetic Property16Coherent Phonon-Mode Excitation in Submicron Single-Crystal Diamond Films with a Graphitized Layer Built-In5Zwitterionic Manganese and Gadolinium Metal–Organic Frameworks as Efficient Contrast Agents for in Vivo Magnetic Resonance Imaging76Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 468A facile synthesis of two new IR optical perovskites based on 1,4-diazabicyclo[2,2,2]octane with a high laser damage threshold7New strategy for designing promising mid-infrared nonlinear optical materials: narrowing the band gap for large nonlinear optical efficiencies and reducing the thermal effect for a high laser-induced damage threshold142Remarkable multimember-ring configurations in a new family of Na 7 M II Sb 5 S 12 (M II = Zn, Cd, Hg) exhibiting various three-dimensional tunnel structures25Structural 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)13Electronic, bonding, linear, and nonlinear optical properties of Na2MGe2Q6 (M=Cd, Zn, Hg; Q=S, Se), Na2ZnSi2S6, and Na2ZnSn2S6 two metal-mixed chalcogenide compounds: Insights from an ab initio study21Synthesis, Crystal Structures, Optical Properties and Theoretical Calculations of Two Metal Chalcogenides Ba2AlSbS5 and Ba2GaBiSe59Multinary metal chalcogenides with tetrahedral structures for second-order nonlinear optical, photocatalytic, and photovoltaic applications183LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials88TlInGe2S6, A Prospective Nonlinear Optical Material: First-Principles DFT Calculations of the Electronic Structure and Optical Properties14Cation substitution inducing gap changes and covalent interaction flexibility enhancing second harmonic generation responses in d10 metal chalcogenides11Synthesis and Characterization of Ag2MnSnS4, a New Diamond‐like Semiconductor14Second-order nonlinear optical properties of CuGa In1-Se2 (x = 0.54): Experimental and theoretical investigations4A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances253Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination26Electronic band structure and basic optical constants of TlGaSn2Se6, a promising NLO semiconductor: First-principles calculations under DFT framework12A 2 SrM IV S 4 (A = Li, Na; M IV = Ge, Sn) concurrently exhibiting wide bandgaps and good nonlinear optical responses as new potential infrared nonlinear optical materials78Ba 4 (BS 3 S) 2 S 4 : a new thioborate with unprecedented [BS 3 -S] and [S 4 ] fundamental building blocks19From CuFeS 2 to Ba 6 Cu 2 FeGe 4 S 16 : rational band gap engineering achieves large second-harmonic-generation together with high laser damage threshold22Li 2 ZnGeS 4 : a promising diamond-like infrared nonlinear optical material with high laser damage threshold and outstanding second-harmonic generation response43Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 913Growth and physicochemical investigations on wide bandgap 2D polymeric amino acetic acid sulfato dilithium metal–organic framework1Crystal structure and second harmonic generation in Bi2TeO5: An X-N study from synchrotron and neutron diffraction data8Sn 2 Ga 2 S 5 : A Polar Semiconductor with Exceptional Infrared Nonlinear Optical Properties Originating from the Combined Effect of Mixed Asymmetric Building Motifs81Solvothermal syntheses, characterizations and semiconducting properties of four quaternary thioargentates Ba2AgInS4, Ba3Ag2Sn2S8, BaAg2MS4 (M = Sn, Ge)21Rb10Zn4Sn4S17: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue28Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance172Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance40Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu3MS4 (M = In, Ga) and BaCu2MS4 (M = Sn, Ge)27Nonlinear Optical Crystals for Second Harmonic Generation19Rational design of infrared nonlinear optical chalcogenides by chemical substitution287A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties59New quaternary chalcogenide Ba 4 HgAs 2 S 10 originating from the combination of linear [HgS 2 ] 2− and tetrahedral [AsS 4 ] 3− modules8Infrared Nonlinear Optical Polymorphs α- and β-SrCu 2 SnS 4 Exhibiting Large Second Harmonic Generation Responses with Requisite Phase-Matching Behavior44Effects of oxygen variation on the improved structural stability, electronic and optical properties of ZnTeO compounds5One-Dimensional Double Chains in Sodium-Based Quaternary Chalcogenides Displaying Intriguing Red Emission and Large Optical Anisotropy17Mild solvothermal syntheses and characterizations of two layered sulfides Ba2Cu2Cd2S5 and Ba3Cu4Hg4S915Cd4SiQ6 (Q = S, Se): Ternary Infrared Nonlinear Optical Materials with Mixed Functional Building Motifs21Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials164Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials55LiBa4Ga5Q12 (Q = S, Se): Noncentrosymmetric Metal Chalcogenides with a Cesium Chloride Topological Structure Displaying a Remarkable Laser Damage Threshold32HgCuPS4: An Exceptional Infrared Nonlinear Optical Material with Defect Diamond-like Structure146Ab initio prediction of the elastic, electronic and optical properties of a new family of diamond-like semiconductors, Li2HgMS4 (M = Si, Ge and Sn)34Syntheses and crystal structures of the quaternary thiogermanates Cu4FeGe2S7and Cu4CoGe2S74Fabrication, Characterization and Optical Investigation of Semi-organic Nonlinear Alanine Hippurate Single Crystals6Mild solvothermal syntheses and characterizations of four quaternary layered sulfides AAgCdS2 (A = K, Rb, Cs) and Cs2Cu2Cd2S413α‑Li2ZnGeS4: A Wide-Bandgap Diamond-like Semiconductor with Excellent Balance between Laser-Induced Damage Threshold and Second Harmonic Generation Response158Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties166Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties29Recent Advances in Oxide‐based Nonlinear Optical Materials with Wide Infrared Transparency Beyond 6 μm38Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li 4 CdSn 2 S 779From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response68Aliovalent-cation-substitution-induced structure transformation: a new path toward high-performance IR nonlinear optical materials47Balanced infrared nonlinear optical performance achieved by modulating the covalency and ionicity distributions in the electron localization function map42Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering145Cu 4 MnGe 2 S 7 and Cu 2 MnGeS 4 : two polar thiogermanates exhibiting second harmonic generation in the infrared and structures derived from hexagonal diamond22Na 4 SnS 4 and Na 4 SnSe 4 exhibiting multifunctional physicochemical performances as potential infrared nonlinear optical crystals and sodium ion conductors27Structural diversities in centrosymmetric La 8 S 4 Cl 8 La 12 S 8 Cl 4 [SbS 3 ] 8 and non-centrosymmetric Ln 12 S 8 Cl 8 [SbS 3 ] 4 (Ln = La and Ce): syntheses, crystal and electronic structures, and optical properties10Unique Unilateral-Chelated Mode-Induced d–p−π Interaction Enhances Second-Harmonic Generation Response in New Ln3LiMS7 Family41Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure25AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds34Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap214Li4MgGe2S7: The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap16Stepwise Li Substitution Induced Structure Evolution and Improved Nonlinear Optical Performance for Diamond-like Sulfides28Highly 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 847Triclinic Layered A2ZnSi3S8 (A = Rb and Cs) with Large Optical Anisotropy and Systematic Research on the Inherent Structure–Performance Relationship in the A2MIIBMIV3Q8 Family11Synthesis, structure, linear and nonlinear optical properties of noncentrosymmetric quaternary diamond-like semiconductors, Cu2ZnGeSe4 (CZGSe) and the novel Cu4ZnGe2Se720Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Syntheses, Structures and Properties of Alkali and Alkaline Earth Metal Diamond-Like Compounds Li2MgMSe4 (M = Ge, Sn)12Superior Infrared Nonlinear Optical Performance Achieved by Synergetic Functional Motif and Vacancy Site Modulations48Building-block approach to the discovery of Na8Mn2(Ge2Se6)2: A polar chalcogenide exhibiting promising harmonic generation signals with a high laser-induced damage threshold9Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63Rational combination of multiple structural groups on regulating nonlinear optical property in hexagonal Ln3MGeS7 polar crystals10First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials19Homovalent Cation Substitutions Leading to New Lithium-Containing La3cusis7 Family Members Having Chiral, Uniaxial Structures and Exhibiting Second- and Third-Harmonic Generation7Li-Free ternary sulphide Cs 5 Ga 9 S 16 with excellent nonlinear optical performance similar to classic LiGaS 213New Quaternary Sulfide LiGaSiS 4: Synthesis, Structure and Optical Properties0Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d10 Metal; M: Main Group Metal; Q: Chalcogen) System44SrZnSnSe4: A quaternary selenide with large second harmonic generation and birefringence40The Role of Electrocatalysts in the Development of Gigawatt-Scale PEM Electrolyzers139New quaternary sulfide LiGaSiS4: Synthesis, structure and optical properties0

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  1. Optical Nonlinearity in Cu2CdSnS4 and α/β-Cu2ZnSiS4: Diamond-like Semiconductors with High Laser-Damage Thresholds

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  2. ChemInform Abstract: Li2CdGeS4, a Diamond‐Like Semiconductor with Strong Second‐Order Optical Nonlinearity in the Infrared and Exceptional Laser Damage Threshold.

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  3. Highly efficient infrared optical nonlinearity of a wide-bandgap chalcogenide Li_2CdGeS_4

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  4. Syntheses and characterization of one-dimensional alkali metal antimony(III) thiostannates(IV), A2Sb2Sn3S10 (A=K, Rb, Cs)

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  5. Field-Induced Spin-Flop in Antiferromagnetic Semiconductors with Commensurate and Incommensurate Magnetic Structures: Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS)

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  31. A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS7

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  44. The first quaternary diamond-like semiconductor with 10-membered LiS 4 rings exhibiting excellent nonlinear optical performances

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  46. 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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  48. Wide band gap design of new chalcogenide compounds: KSrPS 4 and CsBaAsS 4

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