Single crystal of lithium potassium sulphate, a nonlinear optical material, was grown from aqua solution by slow evapo- ration method at room temperature. The cell parameters were estimated by single crystal X-ray dif...Single crystal of lithium potassium sulphate, a nonlinear optical material, was grown from aqua solution by slow evapo- ration method at room temperature. The cell parameters were estimated by single crystal X-ray diffraction analysis. The optical transmittance of the crystal was recorded using the UV-Vis-NIR spectrophotometer and the optical band gap was calculated using this method. The second harmonic generation efficiency was measured by Kurtz and Perry powder technique and the phase-matching property was confirmed. The hardness of the material was measured by Vicker’s hardness test.展开更多
A series of new acentric fluoroborophosphates,namely,RbBPO_(4)F,CsBPO_(4)F and(NH_(4))_(2)BPO_(4)F_(2),have been obtained by combining BO_(3)F or BO_(2)F_(2)with a PO_(4)tetrahedron.The structures of the isomeric RbBP...A series of new acentric fluoroborophosphates,namely,RbBPO_(4)F,CsBPO_(4)F and(NH_(4))_(2)BPO_(4)F_(2),have been obtained by combining BO_(3)F or BO_(2)F_(2)with a PO_(4)tetrahedron.The structures of the isomeric RbBPO_(4)F and CsBPO_(4)F feature a three-dimensional diamond framework,in which a BO_(3)F(or PO_(4))tetrahedron corner is shared with three PO_(4)(or BO_(3)F)tetrahedra,forming 1D tunnels of eight-membered rings(MRs)along the three axial directions,which are filled with alkali cations.(NH_(4))_(2)BPO_(4)F_(2)exhibits a 3D supramolecular structure,in which 1D[BPO_(4)F_(2)]^(1-)anionic chains along the a axes based on cornersharing and alternating PO_(4)and BO_(2)F_(2)tetrahedra are further interconnected with ammonium cations by electrostatic attractions and hydrogen bonds.RbBPO_(4)F,CsBPO_(4)F and(NH_(4))_(2)BPO_(4)F_(2)display second-harmonic generation(SHG)signals approximately 0.4,0.6 and 0.8 times that of KH_(2)PO_(4)(KDP)and exhibit short UV absorption edges(<200 nm).Measurements of thermal stability and optical properties and theoretical calculations have also been performed.展开更多
Sodium paranitrophenolate dihydrate (NPNa·2H2O) is an excellent semiorganic nonlinear optical (NLO) material, crystallizes both in water and methanol with high degree of transparency. Good optical quality single ...Sodium paranitrophenolate dihydrate (NPNa·2H2O) is an excellent semiorganic nonlinear optical (NLO) material, crystallizes both in water and methanol with high degree of transparency. Good optical quality single crystals of dimension upto 18 mm×6 mm×3 mm are obtained by isothermal solvent evaporation technique. The solubility of the crystal in different solvents was measured gravimetrically. The single crystals of NPNa·2H2O show variation in physical properties and growth rate in different solvents. Methanol or ethanol solution yields crystals of bipyramidal shape with clear morphology. However, methanol grown crystal is exhibiting improved hardness parameters and possesses excellent thermal stability as compared to water grown crystals. The effects of solvent on hardness parameter along with thermal and optical properties of NPNa·2H2O was revealed in this paper.展开更多
A series of novel inclusion compounds with compositions of RE(HCO 2) 3(HNO 2)(H 2CO 2) (RE=Y, Tb, Dy, Ho, Er, Yb, Tm) were synthesized and structures were characterized by X ray methods. The orthorhombic structu...A series of novel inclusion compounds with compositions of RE(HCO 2) 3(HNO 2)(H 2CO 2) (RE=Y, Tb, Dy, Ho, Er, Yb, Tm) were synthesized and structures were characterized by X ray methods. The orthorhombic structure was shown to be a new type with a non centrosymmetric space group (20) C 222 1 by single crystal structure determinations. It is characterized by networks of rare earth centered square anti prisms formed by eight oxygen atoms through bridging carbon and nitrogen atoms. The vip formic acid molecules H 2CO 2 are distributed inside the open tunnels along the crystallographic a axis. The magnetic susceptibility measurements show the heavy rare earth compounds follow the Curie Weiss law and the calculated numbers of Bohr magnetons are consistent with the RE 3+ ions. The yttrium compound shows very weak temperature independent paramagnetism.展开更多
The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with ...The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with elemental analyses, 1H NMR spectra and 13C NMR spectra.展开更多
The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupl...The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupling reaction. Their structures were established with elemental analysis, MS, IR and H NMR spectroscopies. 1展开更多
A series of new fluoro-containing copolymers have been synthesized by a Mitsunobu reaction with 4,4＇-（hexafluoroisopropylidene） bisphenol A（6FBPA） and the corresponding N,N-dihydroxyethylaminoaryl azo or ring-loc...A series of new fluoro-containing copolymers have been synthesized by a Mitsunobu reaction with 4,4＇-（hexafluoroisopropylidene） bisphenol A（6FBPA） and the corresponding N,N-dihydroxyethylaminoaryl azo or ring-locked triene compounds, which have high thermal stability and good solubility in organic solvents.The nonlinear optical（NLO） measurements made by Marker fringe method at 1064 nm indicate that the copolymers embedded with the ring-locked triene and azo chromophores exhibit higher macroscopic nonlinear optical coefficient（70.2 pm/V and 26.5-34.6 pm/V,respectively）.Thermal analysis and UV-visible absorption spectra show that the copolymers have good thermal stability（T_d= 264-319℃） and optical transparency （λ_（max）500 nm）.展开更多
As the core device of all-solid-state laser,infrared(IR)nonlinear optical(NLO)material plays a critical role in exploring new coherent lights by frequency conversion technologies,which are widely used in noninvasive m...As the core device of all-solid-state laser,infrared(IR)nonlinear optical(NLO)material plays a critical role in exploring new coherent lights by frequency conversion technologies,which are widely used in noninvasive medical diagnostics,spectroscopy,environmental monitoring and long-distance laser communication.To satisfy the growing demand of current laser technology in IR regions,high performance NLO materials with large second-harmonic generation(SHG)response,high laser-induced damage threshold(LIDT)and wide transparency range are highly expected.Recently,numerous efforts and advances have been achieved in sulfide system.This review highlights the progress of high-performance sulfide IR NLO materials with a good balance between strong SHG response(≥1.0×AgGaS_(2))and wide band gap(≥3.0 eV)since 2018.The chemical synthesis,crystal structure,optical properties and structure-property relationship of 13 high performance metal sulfide IR NLO materials are summarized and reviewed in detail.Finally,the potential opportunities and challenges in IR NLO materials are discussed.展开更多
Nonlinear optical(NLO)crystals capable of controlling and manipulating light to generate coherent radiation at a variety of difficult-to-access wavelengths are essentially crucial for many high-tech applications,yet t...Nonlinear optical(NLO)crystals capable of controlling and manipulating light to generate coherent radiation at a variety of difficult-to-access wavelengths are essentially crucial for many high-tech applications,yet the rational design of NLO crystals with high-performance remains a great challenge.Herein,inspired by two facts,namely,hetero-anionic structures can effectively integrate the diverse property superiorities of single-anions,and T2-type supertetrahedra can exhibit enhanced polarizability compared to simple tetrahedra.We assembled multiple different[TS_(4)](T=Zn,Sn)tetrahedra to form the hybrid T2-type supertetrahedra and successfully synthesized new hybrid T2-type supertetrahedral IR NLO crystals,Ae_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)(Ae=Sr and Ba),both of which exhibit intriguing NLO properties,including strong second harmonic generation responses(2.8×AgGaS_(2)-3.0×AgGaS_(2)),wide band-gaps(2.81-2.89 eV),high laser-induced damage thresholds(~15×AgGaS_(2)),a broad IR transmission range(up to 14μm),and suitable birefringence(0.048-0.051@1064 nm).More significantly,both exhibit congruent melting behavior,and a high-quality single crystal of Ba_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)with centimeter-level has been successfully grown using the Bridgman method.These findings strongly suggest that Ba_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)holds great promise as an IR NLO crystal,and the strategy for constructing hybrid T2-type supertetrahedra is effective for designing novel high-performance NLO crystals.展开更多
Infrared nonlinear optical(IR-NLO)materials play a vital role in generating IR laser output and have significant applications in the fields of communication,medicine,and security.At present,commercial IR-NLO crystals ...Infrared nonlinear optical(IR-NLO)materials play a vital role in generating IR laser output and have significant applications in the fields of communication,medicine,and security.At present,commercial IR-NLO crystals suffer from various performance drawbacks that constrain their range of applications.Therefore,the pursuit of designing and exploring new IR-NLO materials has emerged as an important avenue for the advancement of the IR laser industry.Benefiting from the various structural compositions,wide energy gaps,sufficient second-harmonic-generation intensities,strong laser-induced damage thresholds and favorable phase matching features,Mg-based IR-NLO materials have attracted wide attention in recent years.However,there has not been a specific review of this attractive family.展开更多
The development of Mn-based infrared nonlinear optical(IR-NLO)materials that concurrently exhibit a large second-harmonic generation response(SHG>1.0×AgGaS_(2))and a wide band gap(E_(g)>3.0 eV)remains a for...The development of Mn-based infrared nonlinear optical(IR-NLO)materials that concurrently exhibit a large second-harmonic generation response(SHG>1.0×AgGaS_(2))and a wide band gap(E_(g)>3.0 eV)remains a formidable challenge.Herein,we demonstrate a partial cation substitution strategy to address this issue,successfully transforming centrosymmetric Sr_(2)GeS_(4)into a novel non-centrosymmetric quaternary sulfide,Sr_(3)MnGe_(2)S_(8).The compound features a three-dimensional framework constructed from corner-sharing[MnS_(4)]and[GeS_(4)]tetrahedra,with Sr_(2)+cations residing in the interstitial spaces.Sr_(3)MnGe_(2)S_(8)achieves an outstanding balance of key IR-NLO properties:it shows a strong SHG response(2.4×AgGaS_(2)at 2050 nm),a high laser-induced damage threshold(13.4×AgGaS_(2)),and a wide E_(g)of 3.06 eV—ranking it among the best-performing Mn-based chalcogenides.Theoretical calculations and structural analysis reveal that the excellent NLO performance originates from the synergistic effects between the two distinct types of functional units.This work provides a valuable paradigm for designing high-performance IR-NLO materials through rational structural transformation,highlighting the power of chemical substitution in overcoming property trade-offs.展开更多
Alike phosphates,silicates and germanates exclusively containing tetrahedral basic building units(BBUs)can also exhibit ultraviolet(UV)even deep-UV transitions.They are important for the design of new UV or deep-UV no...Alike phosphates,silicates and germanates exclusively containing tetrahedral basic building units(BBUs)can also exhibit ultraviolet(UV)even deep-UV transitions.They are important for the design of new UV or deep-UV nonlinear optical(NLO)materials.In this paper,four new alkali metal silicates and germanates,Li2Rb4Si6O15,Li2Cs4Si6O15,Li3Rb3Ge6O15 and Li3Cs3Ge6O15 were successfully synthesized by a high temperature solid state reaction.They obey the general formula of LimAnM6O15(A=Rb,Cs;M=Si,Ge;m+n=6)and all exhibit the Sr2Be2B2O7(SBBO)-like structures.More importantly,Li3Rb3Ge6O15 and Li3Cs3Ge6O15 crystallize in the noncentrosymmetric(NCS)structures and exhibit remarkable phase-matched second harmonic generation(SHG)effect,0.8×KH2PO4(KDP)and 1×KDP,respectively.These indicate that they are potential as UV or deep-UV NLO materials.Furthermore,their optical and NLO properties as well as thermal properties were measured.The structure-property relationships were studied by the dipole moment calculations and the first-principles calculations.展开更多
Infrared(IR)nonlinear optical(NLO)materials have important applications in various fields.However,the development of new IR NLO materials with improved performance remains a huge challenge due to distinct microstructu...Infrared(IR)nonlinear optical(NLO)materials have important applications in various fields.However,the development of new IR NLO materials with improved performance remains a huge challenge due to distinct microstructural requirements between second-harmonic generation(SHG)and band gaps.Herein,two new non-centrosymmetric and polar antiperovskite-type X3BA(A and B=anion or anionic group;X=cation)oxychalcogenides,Ba_(3)S[SnOS_(3)]and[Ba_(2)Sn]S[Ge_(2)O_(7)],were successfully designed and synthesized by chemical substitution.In the structures,the three-dimensional framework is formed by the corner-sharing connection of[SBa_(6)]and[SBa4Sn2]octahedra,respectively.Furthermore,the[SnOS_(3)]groups and[Ge_(2)O_(7)]dimers occupy the framework interstices to form the antiperovskite structure.The theoretical calculations and optical property measurements indicate that the materials exhibit good optical properties,including wide band gaps(3.13–3.60 eV),strong SHG responses(0.8–2.0×AgGaS2(AGS)@2090 nm),high laser-induced damage thresholds(3–5×AGS),and moderate birefringence(0.021–0.074@1064 nm).This work further highlights the potential of the antiperovskite structure for the development of high-performance IR NLO materials.展开更多
Balancing the key performance metrics,such as a large second harmonic generation(SHG)response and a wide band gap,is an extremely important but intractable challenge for the development of infrared(IR)nonlinear optica...Balancing the key performance metrics,such as a large second harmonic generation(SHG)response and a wide band gap,is an extremely important but intractable challenge for the development of infrared(IR)nonlinear optical(NLO)materials.Herein,we report two new polymorphs of BaGa_(4)S_(7),β-andγ-BaGa_(4)S_(7),both of which crystallize in the noncentrosymmetric and polar space groups,Pmc2_(1)(No.26)forβ-BaGa_(4)S_(7)and Cm(No.8)forγ-BaGa_(4)S_(7).They show an interesting structural evolution from AA’[Ga_(6)S_(16)]_(∞)chains to AA’A’A[Ga_(6)S_(16)]_(∞)chains to AAA’AAA’[Ga_(6)S_(16)]_(∞)chains as their structures show a tran-sition from the high-temperature phase to the low-temperature phase.More importantly,they both exhibit excellent NLO properties.In particular,β-BaGa_(4)S_(7)exhibits the best balance along with a large phase-matching SHG response(1.2×AgGaS_(2))and a wide band gap(3.94 eV).These indicate thatβ-BaGa_(4)S_(7)will be a promising IR NLO crystal for high-power laser application.The research also provides an insight into exploring new IR NLO crystals based on structural rearrangement.展开更多
Recently,impressive progress has been achieved on a new and brilliant scheme for a solid-state quadratic nonlinear optical(NLO)switch,which holds enormous potential for developing next-generation intelligent optoelect...Recently,impressive progress has been achieved on a new and brilliant scheme for a solid-state quadratic nonlinear optical(NLO)switch,which holds enormous potential for developing next-generation intelligent optoelectronic devices.However,most of them are still restricted by their poor switching capability and low operating temperature.Herein,we present a rational design approach for developing a highly efficient hybrid halide NLO switching material through introducing conjugated aromatic Schiff base cations.As expected,an organic-inorganic hybrid halide compound(C_(10)H_(14)N)PbBr_(3)(1,C_(10)H_(14)N is N-propylbenzylideneaminium)has been developed,which exhibits highly efficient modulation of the quadratic NLO property(1.05 times that of KH_(2)PO_(4))and a high phase transition temperature of 411 K.Besides,the second harmonic generation(SHG)powder test demonstrates that this material is phase matchable.Microscopic single-crystal structure analysis combined with theoretical calculations reveals that the high-performance NLO switching behaviour of 1 originates from the reversible ordered/disordered transformation of the aromatic Schiff base N-propylbenzylideneaminium cations accompanied by the re-orientation of the inorganic[PbBr_(3)]_(∞)framework.More importantly,further investigations show that the conjugated effect of the Schiff base cations makes important contributions to the NLO properties of 1.This work opens up a new route for designing highly efficient quadratic NLO switches and provides a promising way to further develop high-performance solid-state phase transition materials(e.g.ferroelectrics)and intelligent optoelectronic devices.展开更多
文摘Single crystal of lithium potassium sulphate, a nonlinear optical material, was grown from aqua solution by slow evapo- ration method at room temperature. The cell parameters were estimated by single crystal X-ray diffraction analysis. The optical transmittance of the crystal was recorded using the UV-Vis-NIR spectrophotometer and the optical band gap was calculated using this method. The second harmonic generation efficiency was measured by Kurtz and Perry powder technique and the phase-matching property was confirmed. The hardness of the material was measured by Vicker’s hardness test.
基金National Natural Science Foundation of China(No.21875248,91622112,and 21701173)Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)100 Talents Project of Fujian Province。
文摘A series of new acentric fluoroborophosphates,namely,RbBPO_(4)F,CsBPO_(4)F and(NH_(4))_(2)BPO_(4)F_(2),have been obtained by combining BO_(3)F or BO_(2)F_(2)with a PO_(4)tetrahedron.The structures of the isomeric RbBPO_(4)F and CsBPO_(4)F feature a three-dimensional diamond framework,in which a BO_(3)F(or PO_(4))tetrahedron corner is shared with three PO_(4)(or BO_(3)F)tetrahedra,forming 1D tunnels of eight-membered rings(MRs)along the three axial directions,which are filled with alkali cations.(NH_(4))_(2)BPO_(4)F_(2)exhibits a 3D supramolecular structure,in which 1D[BPO_(4)F_(2)]^(1-)anionic chains along the a axes based on cornersharing and alternating PO_(4)and BO_(2)F_(2)tetrahedra are further interconnected with ammonium cations by electrostatic attractions and hydrogen bonds.RbBPO_(4)F,CsBPO_(4)F and(NH_(4))_(2)BPO_(4)F_(2)display second-harmonic generation(SHG)signals approximately 0.4,0.6 and 0.8 times that of KH_(2)PO_(4)(KDP)and exhibit short UV absorption edges(<200 nm).Measurements of thermal stability and optical properties and theoretical calculations have also been performed.
文摘Sodium paranitrophenolate dihydrate (NPNa·2H2O) is an excellent semiorganic nonlinear optical (NLO) material, crystallizes both in water and methanol with high degree of transparency. Good optical quality single crystals of dimension upto 18 mm×6 mm×3 mm are obtained by isothermal solvent evaporation technique. The solubility of the crystal in different solvents was measured gravimetrically. The single crystals of NPNa·2H2O show variation in physical properties and growth rate in different solvents. Methanol or ethanol solution yields crystals of bipyramidal shape with clear morphology. However, methanol grown crystal is exhibiting improved hardness parameters and possesses excellent thermal stability as compared to water grown crystals. The effects of solvent on hardness parameter along with thermal and optical properties of NPNa·2H2O was revealed in this paper.
文摘A series of novel inclusion compounds with compositions of RE(HCO 2) 3(HNO 2)(H 2CO 2) (RE=Y, Tb, Dy, Ho, Er, Yb, Tm) were synthesized and structures were characterized by X ray methods. The orthorhombic structure was shown to be a new type with a non centrosymmetric space group (20) C 222 1 by single crystal structure determinations. It is characterized by networks of rare earth centered square anti prisms formed by eight oxygen atoms through bridging carbon and nitrogen atoms. The vip formic acid molecules H 2CO 2 are distributed inside the open tunnels along the crystallographic a axis. The magnetic susceptibility measurements show the heavy rare earth compounds follow the Curie Weiss law and the calculated numbers of Bohr magnetons are consistent with the RE 3+ ions. The yttrium compound shows very weak temperature independent paramagnetism.
文摘The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene- 1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with elemental analyses, 1H NMR spectra and 13C NMR spectra.
文摘The novel organometallic compounds, 3-[4'(or 2')-(4''-fluorophenyl)] phenyl-1-ferroc- enyl-2-propen-1-ones 5 were synthesized for nonlinear optical chromophores by Pd (0) catalyzed Suzuki cross-coupling reaction. Their structures were established with elemental analysis, MS, IR and H NMR spectroscopies. 1
基金supported by the National Natural Science Foundation(No20774039)the National Basic Research Program of China(No2007CB925103)
文摘A series of new fluoro-containing copolymers have been synthesized by a Mitsunobu reaction with 4,4＇-（hexafluoroisopropylidene） bisphenol A（6FBPA） and the corresponding N,N-dihydroxyethylaminoaryl azo or ring-locked triene compounds, which have high thermal stability and good solubility in organic solvents.The nonlinear optical（NLO） measurements made by Marker fringe method at 1064 nm indicate that the copolymers embedded with the ring-locked triene and azo chromophores exhibit higher macroscopic nonlinear optical coefficient（70.2 pm/V and 26.5-34.6 pm/V,respectively）.Thermal analysis and UV-visible absorption spectra show that the copolymers have good thermal stability（T_d= 264-319℃） and optical transparency （λ_（max）500 nm）.
基金supported by the High-level Talent Project of Xinjiang Uygur Autonomous Region(2020000039)National Natural Science Foundation of China(52002398,61835014,51972336)Xinjiang Key Laboratory of Electronic Information Materials and Devices(2017D04029).
文摘As the core device of all-solid-state laser,infrared(IR)nonlinear optical(NLO)material plays a critical role in exploring new coherent lights by frequency conversion technologies,which are widely used in noninvasive medical diagnostics,spectroscopy,environmental monitoring and long-distance laser communication.To satisfy the growing demand of current laser technology in IR regions,high performance NLO materials with large second-harmonic generation(SHG)response,high laser-induced damage threshold(LIDT)and wide transparency range are highly expected.Recently,numerous efforts and advances have been achieved in sulfide system.This review highlights the progress of high-performance sulfide IR NLO materials with a good balance between strong SHG response(≥1.0×AgGaS_(2))and wide band gap(≥3.0 eV)since 2018.The chemical synthesis,crystal structure,optical properties and structure-property relationship of 13 high performance metal sulfide IR NLO materials are summarized and reviewed in detail.Finally,the potential opportunities and challenges in IR NLO materials are discussed.
基金supported by the National Natural Science Foundation of China(52322202,22071179,52172006,51972230,51890864,51890865)the Natural Science Foundation of Tianjin Municipality(21JCJQJC00090,20JCJQJC00060).
文摘Nonlinear optical(NLO)crystals capable of controlling and manipulating light to generate coherent radiation at a variety of difficult-to-access wavelengths are essentially crucial for many high-tech applications,yet the rational design of NLO crystals with high-performance remains a great challenge.Herein,inspired by two facts,namely,hetero-anionic structures can effectively integrate the diverse property superiorities of single-anions,and T2-type supertetrahedra can exhibit enhanced polarizability compared to simple tetrahedra.We assembled multiple different[TS_(4)](T=Zn,Sn)tetrahedra to form the hybrid T2-type supertetrahedra and successfully synthesized new hybrid T2-type supertetrahedral IR NLO crystals,Ae_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)(Ae=Sr and Ba),both of which exhibit intriguing NLO properties,including strong second harmonic generation responses(2.8×AgGaS_(2)-3.0×AgGaS_(2)),wide band-gaps(2.81-2.89 eV),high laser-induced damage thresholds(~15×AgGaS_(2)),a broad IR transmission range(up to 14μm),and suitable birefringence(0.048-0.051@1064 nm).More significantly,both exhibit congruent melting behavior,and a high-quality single crystal of Ba_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)with centimeter-level has been successfully grown using the Bridgman method.These findings strongly suggest that Ba_(5)Zn_(3)Ga_(2)Sn_(2)S_(15)holds great promise as an IR NLO crystal,and the strategy for constructing hybrid T2-type supertetrahedra is effective for designing novel high-performance NLO crystals.
基金sponsored by the National Natural Science Foundation of China(21771179)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)the Natural Science Foundation of Fujian Province(2022L3092 and 2023H0041).
文摘Infrared nonlinear optical(IR-NLO)materials play a vital role in generating IR laser output and have significant applications in the fields of communication,medicine,and security.At present,commercial IR-NLO crystals suffer from various performance drawbacks that constrain their range of applications.Therefore,the pursuit of designing and exploring new IR-NLO materials has emerged as an important avenue for the advancement of the IR laser industry.Benefiting from the various structural compositions,wide energy gaps,sufficient second-harmonic-generation intensities,strong laser-induced damage thresholds and favorable phase matching features,Mg-based IR-NLO materials have attracted wide attention in recent years.However,there has not been a specific review of this attractive family.
基金supported by the National Natural Science Foundation of China(22175175)Natural Science Foundation of Fujian Province(2022L3092 and 2023H0041)。
文摘The development of Mn-based infrared nonlinear optical(IR-NLO)materials that concurrently exhibit a large second-harmonic generation response(SHG>1.0×AgGaS_(2))and a wide band gap(E_(g)>3.0 eV)remains a formidable challenge.Herein,we demonstrate a partial cation substitution strategy to address this issue,successfully transforming centrosymmetric Sr_(2)GeS_(4)into a novel non-centrosymmetric quaternary sulfide,Sr_(3)MnGe_(2)S_(8).The compound features a three-dimensional framework constructed from corner-sharing[MnS_(4)]and[GeS_(4)]tetrahedra,with Sr_(2)+cations residing in the interstitial spaces.Sr_(3)MnGe_(2)S_(8)achieves an outstanding balance of key IR-NLO properties:it shows a strong SHG response(2.4×AgGaS_(2)at 2050 nm),a high laser-induced damage threshold(13.4×AgGaS_(2)),and a wide E_(g)of 3.06 eV—ranking it among the best-performing Mn-based chalcogenides.Theoretical calculations and structural analysis reveal that the excellent NLO performance originates from the synergistic effects between the two distinct types of functional units.This work provides a valuable paradigm for designing high-performance IR-NLO materials through rational structural transformation,highlighting the power of chemical substitution in overcoming property trade-offs.
基金financially supported by the National Key Research and Development Program of China(2021YFB3601502)the Key Research Program of Frontier Sciences,CAS(ZDBS-LY-SLH035)+6 种基金the National Natural Science Foundation of China(22193044,61835014,51972336)the West Light Foundation of CAS(2019-YDYLTD-002)the Natural Science Foundation of Xinjiang(2021D01E05)the CAS Project for Young Scientists in Basic Research(YSBR-024)Xinjiang Major Science and Technology Project(2021A01001)the CAS President’s International Fellowship Initiative(PIFI,2020PM0046)Tianshan Basic Research Talents(2022TSYCJU0001)。
基金supported by the Natural Science Foundation of Tianjin(19JCZDJC38200)the National Natural Science Foundation of China(51802217,51972230,61835014,51890864 and 51890865)the National Key R&D Program of China(2016YFB0402103)。
文摘Alike phosphates,silicates and germanates exclusively containing tetrahedral basic building units(BBUs)can also exhibit ultraviolet(UV)even deep-UV transitions.They are important for the design of new UV or deep-UV nonlinear optical(NLO)materials.In this paper,four new alkali metal silicates and germanates,Li2Rb4Si6O15,Li2Cs4Si6O15,Li3Rb3Ge6O15 and Li3Cs3Ge6O15 were successfully synthesized by a high temperature solid state reaction.They obey the general formula of LimAnM6O15(A=Rb,Cs;M=Si,Ge;m+n=6)and all exhibit the Sr2Be2B2O7(SBBO)-like structures.More importantly,Li3Rb3Ge6O15 and Li3Cs3Ge6O15 crystallize in the noncentrosymmetric(NCS)structures and exhibit remarkable phase-matched second harmonic generation(SHG)effect,0.8×KH2PO4(KDP)and 1×KDP,respectively.These indicate that they are potential as UV or deep-UV NLO materials.Furthermore,their optical and NLO properties as well as thermal properties were measured.The structure-property relationships were studied by the dipole moment calculations and the first-principles calculations.
基金supported by the National Natural Science Foundation of China(Grant No.52172006 and 52322202)Tianjin Natural Science Foundation(Grant No.21JCJQJC00090).
文摘Infrared(IR)nonlinear optical(NLO)materials have important applications in various fields.However,the development of new IR NLO materials with improved performance remains a huge challenge due to distinct microstructural requirements between second-harmonic generation(SHG)and band gaps.Herein,two new non-centrosymmetric and polar antiperovskite-type X3BA(A and B=anion or anionic group;X=cation)oxychalcogenides,Ba_(3)S[SnOS_(3)]and[Ba_(2)Sn]S[Ge_(2)O_(7)],were successfully designed and synthesized by chemical substitution.In the structures,the three-dimensional framework is formed by the corner-sharing connection of[SBa_(6)]and[SBa4Sn2]octahedra,respectively.Furthermore,the[SnOS_(3)]groups and[Ge_(2)O_(7)]dimers occupy the framework interstices to form the antiperovskite structure.The theoretical calculations and optical property measurements indicate that the materials exhibit good optical properties,including wide band gaps(3.13–3.60 eV),strong SHG responses(0.8–2.0×AgGaS2(AGS)@2090 nm),high laser-induced damage thresholds(3–5×AGS),and moderate birefringence(0.021–0.074@1064 nm).This work further highlights the potential of the antiperovskite structure for the development of high-performance IR NLO materials.
基金supported by the National Natural Science Foundation of China(Grant No.52172006,22071179,51972230,51890864 and 51890865)the Natural Science Foundation of Tianjin(Grant No.20JCJQJC00060 and 21JCJQJC00090).
文摘Balancing the key performance metrics,such as a large second harmonic generation(SHG)response and a wide band gap,is an extremely important but intractable challenge for the development of infrared(IR)nonlinear optical(NLO)materials.Herein,we report two new polymorphs of BaGa_(4)S_(7),β-andγ-BaGa_(4)S_(7),both of which crystallize in the noncentrosymmetric and polar space groups,Pmc2_(1)(No.26)forβ-BaGa_(4)S_(7)and Cm(No.8)forγ-BaGa_(4)S_(7).They show an interesting structural evolution from AA’[Ga_(6)S_(16)]_(∞)chains to AA’A’A[Ga_(6)S_(16)]_(∞)chains to AAA’AAA’[Ga_(6)S_(16)]_(∞)chains as their structures show a tran-sition from the high-temperature phase to the low-temperature phase.More importantly,they both exhibit excellent NLO properties.In particular,β-BaGa_(4)S_(7)exhibits the best balance along with a large phase-matching SHG response(1.2×AgGaS_(2))and a wide band gap(3.94 eV).These indicate thatβ-BaGa_(4)S_(7)will be a promising IR NLO crystal for high-power laser application.The research also provides an insight into exploring new IR NLO crystals based on structural rearrangement.
基金supported by the National Natural Science Foundation of China(22193042,22125110,21833010,22075285,21875251,21921001,U21A2069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024)+2 种基金the Natural Science Foundation of Fujian Province(2020J01112)the Youth Innovation Promotion of Chinese Academy of Sciences(2020307)Young Talent Supporting Project of Fujian Association of Science and Technology(2021000008).
文摘Recently,impressive progress has been achieved on a new and brilliant scheme for a solid-state quadratic nonlinear optical(NLO)switch,which holds enormous potential for developing next-generation intelligent optoelectronic devices.However,most of them are still restricted by their poor switching capability and low operating temperature.Herein,we present a rational design approach for developing a highly efficient hybrid halide NLO switching material through introducing conjugated aromatic Schiff base cations.As expected,an organic-inorganic hybrid halide compound(C_(10)H_(14)N)PbBr_(3)(1,C_(10)H_(14)N is N-propylbenzylideneaminium)has been developed,which exhibits highly efficient modulation of the quadratic NLO property(1.05 times that of KH_(2)PO_(4))and a high phase transition temperature of 411 K.Besides,the second harmonic generation(SHG)powder test demonstrates that this material is phase matchable.Microscopic single-crystal structure analysis combined with theoretical calculations reveals that the high-performance NLO switching behaviour of 1 originates from the reversible ordered/disordered transformation of the aromatic Schiff base N-propylbenzylideneaminium cations accompanied by the re-orientation of the inorganic[PbBr_(3)]_(∞)framework.More importantly,further investigations show that the conjugated effect of the Schiff base cations makes important contributions to the NLO properties of 1.This work opens up a new route for designing highly efficient quadratic NLO switches and provides a promising way to further develop high-performance solid-state phase transition materials(e.g.ferroelectrics)and intelligent optoelectronic devices.
