(Na0.74Ag1.26)BaSnS4: A New AgGaS2-Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold

The development of high-power solid-state lasers is in urgent need of infrared (IR) nonlinear optical (NLO) materials with wide band gaps and high laser-induced damage thresholds (LIDTs). Herein, a new compressed chalcopyrite-like IR NLO crystal (Na_0.74Ag_1.26)BaSnS₄ was successfully synthesized using a facile high-temperature solid-state method. Its structure can be considered as a variant of chalcopyrite AgGaS₂ (AGS)-type ones. It features a three-dimensional framework constructed by corner-sharing {[(Na/Ag)S₄]⁷⁻}_∞ layers and isolated SnS₄ tetrahedra with negative cavities occupied by counter ion Ba²⁺. (Na_0.74Ag_1.26)BaSnS₄ exhibits phase-matchable moderate SHG response (0.31 × AGS), wide band gap (3.70 eV), and high LIDT (6.44 × AGS). Theoretical calculations reveal that the NLO response of (Na_0.74Ag_1.26)BaSnS₄ is mainly originated from the synergetic effects of AgS₄ and SnS₄ tetrahedra, and the inclusion of alkaline and alkaline earth metals is responsible for the wide band gap and high LIDT. Moreover, the discovery of this chalcopyrite-like compound will provide a feasible design strategy for the exploration of new promising IR NLO materials.     

Anionic Aliovalent Substitution from Structure Models of ZnS: Novel Defect Diamond-like Halopnictide Infrared Nonlinear Optical Materials with Wide Band Gaps and Large SHG Effects

To design pnictide nonlinear optical materials with wide band gap and large second-harmonic generation, the heavy halogen I was introduced into pnictides through anionic aliovalent substitution with diamond-like ZnS as templates. Thus, four excellent halopnictide-based infrared nonlinear optical crystals, M^II₃PnI₃ (M^II=Zn, Cd; Pn=P, As), were obtained. They all exhibited defect diamond-like structures with highly parallel-oriented [M^IIPnI₃] mixed-anionic tetrahedral groups, leading to excellent physical properties including wide band gaps (2.38–2.85 eV), large second harmonic generation responses (2.7–5.1×AgGaS₂), high laser-induced damage thresholds (5.5–10.7×AgGaS₂), and good IR transparency. In particular, Cd₃PI₃ and Cd₃AsI₃ achieved phase-matching (Δn=0.035 and 0.031) that their template β-ZnS could not do. Anionic aliovalent substitution provides a feasible strategy to design novel promising halopnictide IR NLO materials.     

Na2BaMQ4 (M=Ge,Sn; Q=S,Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations

Infrared nonlinear optical (IR NLO) materials with excellent performances are particularly important in laser technology. However, to design and synthesize an efficient IR NLO material with a balance between the optical band gap and the NLO coefficient is still a huge challenge. With this in mind, four new IR NLO materials Na₂BaSnS₄, Na₂BaSnSe₄, Na₂BaGeS₄, and Na₂BaGeSe₄ were successfully designed and synthesized. The compounds exhibit excellent properties with a suitable balance of band gap and NLO coefficient measured for Na₂BaSnS₄ (3.27 eV and about 17×KDP, that is, about 17 times that of KH₂PO₄ (KDP)) and Na₂BaGeS₄ (3.7 eV and about 10×KDP), demonstrating that the systems satisfy the key requirements as promising IR NLO candidates. Remarkably, the new compounds also undergo a novel structural transformation from tetragonal to trigonal systems, the first time that this has been reported for quaternary metal chalcogenides.     

Na2BaMQ4 (M=Ge,Sn; Q=S,Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations

Infrared nonlinear optical (IR NLO) materials with excellent performances are particularly important in laser technology. However, to design and synthesize an efficient IR NLO material with a balance between the optical band gap and the NLO coefficient is still a huge challenge. With this in mind, four new IR NLO materials Na₂BaSnS₄, Na₂BaSnSe₄, Na₂BaGeS₄, and Na₂BaGeSe₄ were successfully designed and synthesized. The compounds exhibit excellent properties with a suitable balance of band gap and NLO coefficient measured for Na₂BaSnS₄ (3.27 eV and about 17×KDP, that is, about 17 times that of KH₂PO₄ (KDP)) and Na₂BaGeS₄ (3.7 eV and about 10×KDP), demonstrating that the systems satisfy the key requirements as promising IR NLO candidates. Remarkably, the new compounds also undergo a novel structural transformation from tetragonal to trigonal systems, the first time that this has been reported for quaternary metal chalcogenides.     

Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long-neglected Nitrides and Popular Chalcogenides

Traditional infrared (IR) nonlinear optical (NLO) materials such as AgGaS₂ are crucial to key devices for solid-state lasers, however, low laser damage thresholds intrinsically hinder their practical application. Here, a robust strategy is proposed for unbiased high-throughput screening of more than 140 000 materials to explore novel IR NLO materials with high thermal conductivity and wide band gap which are crucial to intrinsic laser damage threshold. Via our strategy, 106 compounds with desired band gaps, NLO coefficients and thermal conductivity are screened out, including 8 nitrides, 68 chalcogenides, in which Sr₂SnS₄ is synthesized to verify the reliability of our process. Remarkably, thermal conductivity of nitrides is much higher than that of chalcogenides, e.g., 5×AgGaS₂ (5.13 W/m K) for ZrZnN₂, indicating that nitrides could be a long-neglected system for IR NLO materials. This strategy provides a powerful tool for searching NLO compounds with high thermal conductivity.     

Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb,Cs): Synthesis,Characterization and Nonlinear Optical Properties

Two new non‐centrosymmetric polar quaternary selenides, namely, RbZn₄In₅Se₁₂ and CsZn₄In₅Se₁₂, have been synthesized and structurally characterized. They exhibit a 3D diamond‐like framework (DLF) consisting of corner‐shared MSe₄ (M=Zn/In) tetrahedra, in which the A⁺ ions are located. Both compounds are thermally stable up to 1300 K and exhibit large transmittance in the infrared region (0.65–25 μm) with measured optical band gaps of 2.06 eV for RbZn₄In₅Se₁₂ and 2.11 eV for CsZn₄In₅Se₁₂. Inspiringly, they exhibit a good balance between strong second harmonic generation (SHG) efficiency (3.9 and 3.5×AgGaS₂) and high laser‐induced damage thresholds (13.0×AgGaS₂). Theoretical calculations based on density functional theory (DFT) methods confirm that such strong SHG responses originate from the 3D DLF structure.     

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials

To design high‐performance mid‐infrared (mid‐IR) nonlinear optical (NLO) materials, we have focused on the combination of a heavy metal lone pair cation, Pb²⁺ and mixed oxyhalides. A systematic investigation in PbO‐PbCl₂‐PbBr₂ system led us to discover the first examples of NLO lead mixed oxyhalides, namely, Pb₁₃O₆Cl₄Br₁₀, Pb₁₃O₆Cl₇Br₇, and Pb₁₃O₆Cl₉Br₅. All the reported materials have remarkably comprehensive properties including broad IR transparency (up to 14.0 μm), qualified second harmonic generation (SHG) responses (0.6–0.9×AgGaS₂), wide band gaps (3.05–3.21 eV), and ease of crystal growth. Interestingly, a centimeter‐sized single crystal (2.9×1.3×0.5 cm³) of Pb₁₃O₆Cl₉Br₅ revealing a wide transparent range (0.384–14.0 μm) and high laser damage threshold (LDT) (14.6×AgGaS₂) has been successfully grown in an open system. The study suggests that all the reported mixed oxyhalides are outstanding candidates for mid‐IR NLO materials.     

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High-Performance Mid-Infrared Nonlinear Optical Materials

To design high-performance mid-infrared (mid-IR) nonlinear optical (NLO) materials, we have focused on the combination of a heavy metal lone pair cation, Pb²⁺ and mixed oxyhalides. A systematic investigation in PbO-PbCl₂-PbBr₂ system led us to discover the first examples of NLO lead mixed oxyhalides, namely, Pb₁₃O₆Cl₄Br₁₀, Pb₁₃O₆Cl₇Br₇, and Pb₁₃O₆Cl₉Br₅. All the reported materials have remarkably comprehensive properties including broad IR transparency (up to 14.0 μm), qualified second harmonic generation (SHG) responses (0.6–0.9×AgGaS₂), wide band gaps (3.05–3.21 eV), and ease of crystal growth. Interestingly, a centimeter-sized single crystal (2.9×1.3×0.5 cm³) of Pb₁₃O₆Cl₉Br₅ revealing a wide transparent range (0.384–14.0 μm) and high laser damage threshold (LDT) (14.6×AgGaS₂) has been successfully grown in an open system. The study suggests that all the reported mixed oxyhalides are outstanding candidates for mid-IR NLO materials.     

Na2Ba[Na2Sn2S7]: Structural Tolerance Factor-Guided NLO Performance Improvement

The strong mutual coupling of and even the opposite change in the key parameters, such as the band gap (E_g) and second-order harmonic generation (SHG), leads to the extreme scarcity in high-performance IR nonlinear optical (NLO) chalcogenides. Herein, we report 8 new sulfides, Na₂Ba[(Ag_xNa_1−x)₂Sn₂S₇] ( 1 , x=0; 1 series , x=0.1–0.6; Na₂Ba[(Li_0.58Na_0.42)₂Sn₂S₇], 1-0.6Li ); Na₂Sr[Cu₂Sn₂S₇] ( 2 ); and Na₂Ba[Cu₂Sn₂S₇] ( 3 ). We use the structural tolerance factor ( ) to connect the chemical composition, crystal structure, and NLO properties. Guided by these correlations, a better balance between E_g and SHG is realized in 1 , which exhibits a large E_g of 3.42 eV and excellent NLO properties (SHG: 1.5×AGS; laser-induced damage threshold: 12×AGS), representing the best performance among the known Hg- or As-free sulfides to date.     

LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO3

Excellent nonlinear optical materials simultaneously meet the requirements of large SHG response, phase‐matching capability, wide transparency windows, considerable energy band‐gap, good thermal stability and structure stability. Herein, two new promising nonlinear optical (NLO) crystals LiM^II(IO₃)₃ (M^II=Zn and Cd) are rationally designed by the aliovalent substitution strategy from the commercialized α‐LiIO₃ with the perfect parallel alignment of IO₃ groups. Compared with parent α‐LiIO₃ and related A^I₂M^IV(IO₃)₆, the title compounds exhibit more stable covalent 3D structure, and overcome the racemic twinning problem of A^I₂M^IV(IO₃)₆. More importantly, both compounds inherit NLO‐favorable structure merits of α‐LiIO₃ and show larger SHG response (≈14× and ≈12×KDP), shorter absorption edge (294 and 297 nm) with wider energy band‐gap (4.21 and 4.18 eV), good thermal stability (460 and 430 °C), phase‐matching behaviors, wider optical transparency window and good structure stability, achieving an excellent balance of NLO properties.     

Ultrashort Phase-Matching Wavelength and Strong Second-Harmonic Generation in Deep-UV-Transparent Oxyfluorides by Covalency Reduction

The development of urgently-needed ultraviolet (UV)/deep-UV nonlinear optical (NLO) materials has been hindered by contradictory requirements of the microstructure, in particular the need for a strong second-harmonic generation (SHG) response as well as a short phase-matching (PM) wavelength. We herein employ a “de-covalency” band gap engineering strategy to adjust the optical linearity and nonlinearity. This has been achieved by assembling two types of transition-metal (TM) polyhedra ([TaO₂F₄] and [TaF₇]), affording the first tantalum-based deep-UV-transparent NLO materials, A₅Ta₃OF₁₈ (A = K (KTOF), Rb (RTOF)). Experimental and theoretical studies reveal that the highly ionic bonds and strong electropositivity of tantalum in the two oxyfluorides induce record short PM wavelengths (238 (KTOF) and 240 (RTOF) nm) for d⁰-TM-centered oxides, in addition to strong SHG responses (2.8 × KH₂PO₄ (KTOF) and 2.6 × KH₂PO₄ (RTOF)), and sufficient birefringences (0.092 (KTOF) and 0.085 (RTOF) at 546 nm). These results not only broaden the available strategies for achieving deep-UV NLO materials by exploiting the currently neglected d⁰-TMs, but also push the shortest PM wavelength into the short-wavelength UV region.     

BaGa2MQ6 (M = Si, Ge; Q = S, Se): a new series of promising IR nonlinear optical materials

The four compounds BaGa(2)MQ(6) (M = Si, Ge; Q = S, Se) have been identified as a new series of IR nonlinear optical (NLO) materials and are promising for practical applications. They are isostructural and crystallize in the noncentrosymmetric polar space group R3 of the trigonal system. Their three-dimensional framework is composed of corner-sharing (Ga/M)Q(4) (M = Si, Ge; Q = S, Se) tetrahedra with Ba(2+) cations in the cavities. The polar alignment of one (Ga/M)-Q2 bond for each (Ga/M)Q(4) tetrahedra along the c direction is conducive to generating a large NLO response, which was confirmed by powder second-harmonic generation (SHG) using a 2090 nm laser as fundamental wavelength. The SHG signal intensities of the two sulfides were close to that of AgGaS(2) and those for the two selenides were similar as that of AgGaSe(2). The large band gaps of 3.75(2) eV, 3.23(2) eV, 2.88(2) eV, and 2.22 (2) eV for BaGa(2)SiS(6), BaGa(2)GeS(6), BaGa(2)SiSe(6), and BaGa(2)GeSe(6), respectively, will be very helpful to increase the laser damage threshold. Moreover, all the four BaGa(2)MQ(6) (M = Si, Ge; Q = S, Se) compounds exhibit congruent-melting behavior, which indicates that bulk crystals needed for practical applications can be obtained by the Bridgman-Stockbarger method. The calculated birefringence indicates that these materials may be phase-matchable in the IR region and the calculated SHG coefficients agree with the experimental observations. According to our preliminary study, the BaGa(2)MQ(6) compounds represent a new series of promising IR nonlinear optical (NLO) materials which do not belong to the traditional chalcopyrite-type materials such as AgGaQ2 (Q = S, Se) and ZnGeP(2).     

Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts

Inorganic adducts are an emerging class of infrared nonlinear optical (NLO) materials. However, although the reported NLO adducts have sufficient birefringences and significant laser-induced damage thresholds (LIDTs), they commonly suffer from weak second harmonic generation (SHG) responses. In this work, a series of polar phosphorus chalcogenide cage molecules with strong hyperpolarizabilities were theoretically screened out to enhance the SHG responses of adducts. Accordingly, (CuI)₃(P₄S₄), (CuI)₃(P₄Se₄), (CuBr)₇(P₄S₃)₃ and (CuBr)₇(P₄Se₃)₃ with target polar cage molecules were successfully synthesized. As expected, they exhibit enhanced SHG responses while keeping moderate birefringences and high LIDTs. Notably, (CuBr)₇(P₄Se₃)₃ possesses the largest SHG response (3.5×AGS@2.05 μm) among the known inorganic NLO adducts. Our study confirms that introducing NLO-active cage molecules into adducts is an efficient strategy for high-performance NLO materials.     

Designing Silicates as Deep-UV Nonlinear Optical (NLO) Materials using Edge-Sharing Tetrahedra

Discovering new deep-ultraviolet (DUV) nonlinear optical (NLO) materials is currently a great challenge. The reported DUV NLO materials are almost exclusively borates or phosphates. Silicates—the largest constituent of the earth's crust—are excluded owing to their weak second harmonic generation (SHG) response. We report a silicate, Li₂BaSiO₄, with edge-sharing LiO₄–SiO₄ tetrahedra that achieves the balance between a short UV absorption edge, below 190 nm, and a large SHG response, 2.8×KDP. The SHG intensity is the largest for silicates without second-order Jahn–Teller cations, and exceeds that of non-isomorphic Li₂SrSiO₄ by more than an order of magnitude. As such Li₂BaSiO₄ may be seen as a promising DUV-UV NLO material. This research indicates that edge-sharing tetrahedra is a new design parameter for discovering new DUV NLO materials.     

Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties

To develop high-performance nonlinear optical (NLO) materials for infrared (IR) applications, we have applied a rational element-composition design strategy and investigated the unexplored PbO–PbCl₂–PbI₂ system. By doing so, we discovered a new polar lead mixed oxyhalide, Pb₁₈O₈Cl₁₅I₅, the first synthetic metal oxyhalide combining both Cl⁻ and I⁻. Pb₁₈O₈Cl₁₅I₅ reveals an unprecedented structural feature with two different dimensional types of oxocentered Pb–O units, namely, [O₄Pb₈]⁸⁺ clusters and [OPb₂]²⁺ chains. Centimeter-sized single crystals of Pb₁₈O₈Cl₁₅I₅ have been successfully grown under ambient conditions. Remarkably, Pb₁₈O₈Cl₁₅I₅ satisfies all fundamental yet rigorous criteria for high-performance IR NLO materials, exhibiting the widest IR transparency (up to 16.0 μm) among oxide-based crystals, strong second-harmonic generation response (1.05×AgGaS₂), superior birefringence (0.086 at 636 nm), and a high laser-induced damage threshold (8.5×AgGaS₂).     

Sr6Cd2Sb6O7S10: Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups

A new nonlinear optical (NLO) oxysulfide, Sr₆Cd₂Sb₆O₇S₁₀, which contains the functional groups [SbO_xS_5?x]^7? (x=0, 1) with a 5s² electron configuration, is synthesized by a solid‐state reaction. This compound displays a phase‐matchable second harmonic generation (SHG) response four times stronger than AgGaS₂ (AGS) under laser irradiation at 2.09 μm. Single‐crystal‐based optical measurements reveal a SHG intensity that can be tuned by temperature and novel photoluminescence properties. Theoretical analyses demonstrate that tetragonal [SbOS₄]^7? and [SbS₅]^7? pyramids make the predominant contribution to the enhanced SHG effect. Among those, the [SbOS₄]^7? units with mixed anions make a larger contribution. This work proposes that oxysulfide groups with an ns² electron configuration can serve as new functional building units in NLO materials and opens a new avenue for the design of other optoelectronic materials.     

Alkalimetalltetraethinylozincate und ‐cadmate AI2M(C2H)4 (AI = Na — Cs,M = Zn,Cd): Synthese,Kristallstruktur und spektroskopische Eigenschaften

Alkali Metal Tetraethinylozincates and ‐cadmates A^I₂M(C₂H)₄ (A^I = Na — Cs, M = Zn, Cd): Synthesis, Crystal Structures, and Spectroscopic Properties By reaction of A^IC₂H (A^I = Na — Cs) with divalent zinc and cadmium salts in liquid ammonia the alkali metal tetraethinylozincates and ‐cadmates A^I₂M(C₂H)₄ (M = Zn, Cd) were accessible as polycrystalline powders. While Na₂M(C₂H)₄ is amorphous to X‐rays and the crystal structure of Cs₂Zn(C₂H)₄ could not be solved up to now, the remaining compounds are isotypic to the already known crystal structures of the potassium compounds, as was deduced from powder diffraction with X‐rays and synchrotron radiation. They crystallise in the tetragonal space group I4₁a, contain [M(C₂H)₄]^2— tetrahedra and show structural relationships to the scheelit and anatas structure types. Raman spectroscopic investigations confirm the existence of tetrahedral fragments with C‐C triple bonds in the alkali as well as in the amorphous alkaline earth metal compounds A^IIM(C₂H)₄ (A^II = Mg — Ba, M = Zn, Cd).     

Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra

Discovering new deep‐ultraviolet (DUV) nonlinear optical (NLO) materials is currently a great challenge. The reported DUV NLO materials are almost exclusively borates or phosphates. Silicates—the largest constituent of the earth's crust—are excluded owing to their weak second harmonic generation (SHG) response. We report a silicate, Li₂BaSiO₄, with edge‐sharing LiO₄–SiO₄ tetrahedra that achieves the balance between a short UV absorption edge, below 190 nm, and a large SHG response, 2.8×KDP. The SHG intensity is the largest for silicates without second‐order Jahn–Teller cations, and exceeds that of non‐isomorphic Li₂SrSiO₄ by more than an order of magnitude. As such Li₂BaSiO₄ may be seen as a promising DUV‐UV NLO material. This research indicates that edge‐sharing tetrahedra is a new design parameter for discovering new DUV NLO materials.     

Synthesis,Structure and Bonding,Optical Properties of Ba4MTrQ6 (M=Cu,Ag; Tr=Ga,In; Q=S,Se)

Four new quaternary chalcogenides, Ba₄AgGaS₆ ( 1 ), Ba₄AgGaSe₆ ( 2 ), Ba₄CuInS₆ ( 3 ), and Ba₄AgInS₆ ( 4 ), were synthesized by solid‐state reactions and their structures were characterized through single‐crystal X‐ray diffraction. In spite of their similar chemical compositions, the flexible arrangement between the transition metals and the triel atoms leads to subtle differences in their polyanion structures. All structures feature similar [MTrQ₆]^8? 1D polyanionic chains (M=Cu, Ag; Tr=Ga, In; Q=S, Se), which are constructed from corner‐sharing MQ₄ or TrQ₄ tetrahedra. However, the transition metals and triels are mixed in 1 , 2 , and 3 , but they occupy independent crystallographic sites in 4 . As a result, compounds 1 – 3 belong to the known Ba₂CoS₃ (Pnma No. 62) or Ba₂MnS₃ (Pnma No. 62) class, whereas 4 crystallizes in its own structural type within the monoclinic P2₁/c (No. 14) space group. The structural relationship among these new phases was also studied with the aid of DFT calculations and related optical properties are presented as well.     

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

Two mixed‐metal gallium iodate fluorides, namely, α‐ and β‐Ba₂[GaF₄(IO₃)₂](IO₃) ( 1 and 2 ), have been designed by the aliovalent substitutions of α‐ and β‐Ba₂[VO₂F₂(IO₃)₂](IO₃) ( 3 and 4 ) involving one cationic and two anionic sites. Both 1 and 2 display large second‐harmonic generation responses (≈6×KH₂PO₄ (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges (≈0.27–12.5 μm), and high relevant laser‐induced damage thresholds (29.7× and 28.3×AgGaS₂, respectively), which indicates that 1 and 2 are potential second‐order nonlinear optical materials in the ultraviolet to mid‐infrared. Our studies propose that three‐site aliovalent substitution is a facile route for the discovery of good NLO materials.