we have synthesised a series of new optically nonlinear organic materials of cinnamylidene-acetophenone derivatives which have large nonl inear optical susceptibilities and short cut-off wavelengths.
hydroxy-4-nitro azobenzene (NHA) and 4-amino-4-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) mat...hydroxy-4-nitro azobenzene (NHA) and 4-amino-4-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) materials containing NHA and DO3 were synthesized by Sol-Gel process. The preparation and properties of two NLO materials were studied and characterized by FTIR, 1H-NMR, UV-VIS, SEM, DSC and SHG measurements. The results show that the maximum doping amounts of NHA and DO3 in two doped hybrid NLO materials are 7.2(wt)% and 11.3(wt)% respectively, and the corresponding second-order NLO coefficients (d33 values) are 2.91×10 8esu and 6.14×10 8esu. Two doped NLO materials have relatively good RT stability, after 90 days at RT the d33 values can maintain about 85% of their initial values, but after 10h at 100℃ can only maintain about 50% of their initial values. In this report, the reasons for high-temperature instability of doped materials were discussed, and the possible improvements were also suggested.展开更多
The simultaneous achievement of wide band gap and strong nonlinear optical(NLO)effect poses a challenging task in the development of infrared(IR)NLO materials.The coupling strategy of polyhedral building blocks has be...The simultaneous achievement of wide band gap and strong nonlinear optical(NLO)effect poses a challenging task in the development of infrared(IR)NLO materials.The coupling strategy of polyhedral building blocks has been demonstrated to be one of the effective approaches for constructing superior optical materials with well-balanced performance.Here,a new family of IR NLO materials A^(I)_(2)Mg_(3)Ga_(12)S_(22)(AI=K,Rb)that first contain[MgS_(6)]octahedra and T2-type supertetrahedra was designed and synthesized.K_(2)Mg_(3)Ga_(12)S_(22) exhibits a wide band gap of 3.34 eV,and a moderate second-harmonic generation response intensity of 0.4 times that of AgGaS2 under 2µm Q-switched laser radiation.Furthermore,the birefringence of K_(2)Mg_(3)Ga_(12)S_(22) is calculated to be 0.028@1064 nm,resulting in favorable phase-matching behavior in IR region.These characteristics suggest that K_(2)Mg_(3)Ga_(12)S_(22) could be a promising material for nonlinear frequency conversion applications and it provides new ideas into the design of novel compounds with outstanding IR NLO performances.展开更多
To rationalize the design of D-π-A type organic small-molecule nonlinear optical materials,a theory guided machine learning framework is constructed.Such an approach is based on the recognition that the optical prope...To rationalize the design of D-π-A type organic small-molecule nonlinear optical materials,a theory guided machine learning framework is constructed.Such an approach is based on the recognition that the optical property of the molecule is predictable upon accumulating the contribution of each component,which is in line with the concept of group contribution method in thermodynamics.To realize this,a Lewis-mode group contribution method(LGC)has been developed in this work,which is combined with the multistage Bayesian neural network and the evolutionary algorithm to constitute an interactive framework(LGC-msBNN-EA).Thus,different optical properties of molecules are afforded accurately and efficientlyby using only a small data set for training.Moreover,by employing the EA model designed specifically for LGC,structural search is well achievable.The origins of the satisfying performance of the framework are discussed in detail.Considering that such a framework combines chemical principles and data-driven tools,most likely,it will be proven to be rational and efficient to complete mission regarding structure design in related fields.展开更多
How to obtain organic electro-optic materials with large electro-optic coefficients,high glass transition temperature,and good optical transparency remains a challenge in this field.To solve this problem,we introduce ...How to obtain organic electro-optic materials with large electro-optic coefficients,high glass transition temperature,and good optical transparency remains a challenge in this field.To solve this problem,we introduce groups that can undergo Huisgen cycloaddition reactions into the donor and electron bridge of chromophores with large hyperpolarizability using tetrahydroquinoline as the donor.Binary cross-linkable chromophores TLD1-2 with CF_(3)-TCF as the acceptor and chromophores TLD3-4 with 5Fph-TCF as the acceptor were synthesized.After poling and crosslinking,the T_(g)of TLD1/TLD2 and TLD3/TLD4 were raised to 152 and 174°C,respectively.The electro-optical coefficients of chromophores TLD1/TLD2 and TLD3/TLD4 were as high as 312 pm/V and 287 pm/V,respectively.The long-term alignment stability test showed that after being left at 85℃ for 500 h,the cross-linked film TLD3/TLD4 can still maintain more than 98%of the original electro-optical coefficient value,which is higher than that of TLD1/TLD2(93%).The chromophore TLD3-4 exhibited much blue-shifted maximum absorption wavelengths(~40 nm)compared to TLD1-2 which was beneficial for reducing optical loss in the device.The combination of high electro-optic coefficient,strong stability,and excellent optical transparency makes the TLD series of binary cross-linked materials very promising for practical high-performance electro-optic devices.展开更多
Exploration of new infrared(IR) nonlinear optical(NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formida...Exploration of new infrared(IR) nonlinear optical(NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation(SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d^0 transition metal fluorooxofunctional groups for designing mid-IR NLO materials. By studying a series of d^0 transition metal oxyfluorides(TMOFs),the influences of fluorooxo-functional groups with different d^0 configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d^0 configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d^0 TMOFs exhibit wide band gaps(all the band gaps >3.0 e V), large birefringence Δn(> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d^0 TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap.展开更多
Three new complex borate compounds K7CaBi2B15O30,K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space gr...Three new complex borate compounds K7CaBi2B15O30,K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space group R32,while K7BaBi2B15O30 crystallizes in the noncentrosymmetric orthorhombic polar space group Pca21.All of the title compounds have similar three-dimensional crystal structures,which are composed of isolated B5 O10 groups and LaO6 or BiO6 octahedra,and K^+,Ca^2+,and Ba^2+cations fill into the cavities to keep charge balance.Based on our research,in the system of K7 MIIRE2 B15O30(MII=Ca,Sr,Ba,Zn,Cd,Pb,K/RE0.5;RE=Sc,Y,La,Gd,Lu,Bi),K7BaBi2B15O30 is unique and crystallizes in a different space group,which enriches the structural chemistry of borate.Detailed structural analyses indicate that the structural variation is due to the difference in size and coordination number of the alkaline-earth metal cations.Besides,UV-Vis-NIR spectroscopy analysis and the second-harmonic generation(SHG)measurement on the powder samples show that K7CaBi2B15O30 exhibits a UV cutoff edge(about 282 nm)and a moderate SHG response(about 0.6×KDP).In addition,thermal analysis and infrared spectroscopy were also presented.To better understand the structure-property relationships of the title compounds,the first-principles calculations have been performed.展开更多
The nonlinear optical （NLO） and optical limiting （OL） properties of three new structures of organic NLO vip host Poly（N-vinylcarbozole）/disperse orange 3 （PVK/DO3）, PVK/disperse orange 13 （PVK/DO13）. and P...The nonlinear optical （NLO） and optical limiting （OL） properties of three new structures of organic NLO vip host Poly（N-vinylcarbozole）/disperse orange 3 （PVK/DO3）, PVK/disperse orange 13 （PVK/DO13）. and PVK/disperse orange 25 （PVK/DO25） as a solution at different concentrations and as a thin-film sample are studied using continuous wave z-scan system at 532 nm. The open-aperture z-scan data of the NLO materials in the solution and thin-film samples displayed two-photon and saturable absorptions, respectively. The PVK/DO13 exhibites the largest and best values of the nonlinearities, such as n2, β, X（3） compared with those of PVK/DO3 and PVK/DO25. This nonlinearity increases as the concentration increases. Tile results indicate that these NLO materials are good candidates for optical switching and OL devices.展开更多
Employing unsymmetrical 2-mercapto-5-methyl-1,3,4-thiadiazole and 2,2′-bipyridine as mixed ligands, a new low-dimensional coordination polymer [Zn(MMTA) 2 (2,2′-bipy)] n (MMTA = 2-mercapto-5-methyl-1,3,4-thiadiazole...Employing unsymmetrical 2-mercapto-5-methyl-1,3,4-thiadiazole and 2,2′-bipyridine as mixed ligands, a new low-dimensional coordination polymer [Zn(MMTA) 2 (2,2′-bipy)] n (MMTA = 2-mercapto-5-methyl-1,3,4-thiadiazole, 2,2′-bipy = 2,2′-bipyridine), has been synthesized under solvothermal condition and characterized by single crystal X-ray diffraction. This compound crys- tallizes in the noncentrosymmetric space group Cc, with cell parameters: a = 8.291(4) , b = 15.483(9) , c = 15.620(6) , = 96.00(5)°, V = 1994.1(2) 3 , and Z = 4. The mixed ligands link the zinc center into a mononuclear unit, which is futher linked by weak C-H···N and C-H···S hydrogen bonds into a three-dimensional noncentrosymmetric framework. The compound exhibits intense photoluminescence and distinct NLO properties at room temperature. The intensity of the green light produced by the powder sample of the compound is about 3.2 times that produced by KDP powder. On the basis of the results of TG analysis, the structure is thermally stable up to ～260 °C.展开更多
Ultraviolet(UV)nonlinear optical(NLO)crystal materials are hailed as the"chip"of the optoelectronic industry for they play a unique and crucial role in many newly developed scientific and technological appli...Ultraviolet(UV)nonlinear optical(NLO)crystal materials are hailed as the"chip"of the optoelectronic industry for they play a unique and crucial role in many newly developed scientific and technological applications.At present,due to the relatively single frequency doubling gene types of traditional NLO materials,the service performance of UV NLO materials is fundamentally restricted.Therefore,there is an urgent need to develop new synthesis methods,search for novel functional groups,expand new UV NLO materials systems,screen new high-performance crystals,and then break through performance bottlenecks.Herein,we review the recent progresses on UV NLO crystal materials.Furthermore,we prospect that these recently developed approaches will continuously extend their advantages in developing superior UV NLO materials in the near future.展开更多
Nonlinear optical(NLO)material are of great importance in converting the frequency to extend the laser spectrum in mid-and far-infrared(IR)regions where lasers operate poorly or are unavailable.However,the contradicti...Nonlinear optical(NLO)material are of great importance in converting the frequency to extend the laser spectrum in mid-and far-infrared(IR)regions where lasers operate poorly or are unavailable.However,the contradiction between large second-harmonic generation(SHG)intensity and wide band gap(E_(g))is a long-standing problem for IR NLO materials.To address the issue,metal chalcogenides have been successfully synthesized and developed excellent optical properties in the past few decades.As a newly discovered category of chalcogenides,salt-inclusion chalcogenides with distinctive structures and brilliant performances have been placed great expecta-tions to be a novel problem-solving.In this review,52 compounds in this thriving family are categorized via dimensions of host and vip parts,further discussing the relationships between their structures and NLO properties,as well as future perspectives of this family.展开更多
We report a simple solution-processed method for the fabrication of low-cost,flexible optical limiting materials based on graphene oxide(GO) impregnated polyvinyl alcohol(PVA) sheets.Such GO–PVA composite sheets disp...We report a simple solution-processed method for the fabrication of low-cost,flexible optical limiting materials based on graphene oxide(GO) impregnated polyvinyl alcohol(PVA) sheets.Such GO–PVA composite sheets display highly efficient broadband optical limiting activities for femtosecond laser pulses at 400,800,and 1400 nm with very low limiting thresholds.Femtosecond pump–probe measurement results revealed that nonlinear absorption played an important role for the observed optical limiting activities.High flexibility and efficient optical limiting activities of these materials allow these composite sheets to be attached to nonplanar optical sensors in order to protect them from light-induced damage.展开更多
Metal iodates containing I(Ⅴ)with lone electron pairs in an asymmetric coordination geometry exhibit excellent second-harmonic generation(SHG)responses,wide transmission range and large band gaps.During the past ten ...Metal iodates containing I(Ⅴ)with lone electron pairs in an asymmetric coordination geometry exhibit excellent second-harmonic generation(SHG)responses,wide transmission range and large band gaps.During the past ten years,metal iodates have been widely studied,and introducing large electronegative fluorine atoms into metal iodates has also attracted much attention.These F-containing iodates are different from pure iodates in terms of composition,symmetry and transmittance.Especially because oxide-fluoride heterolepic anion groups can exhibit interesting structure-directing properties,e.g.trans-and cis-directing properties,these F-containing iodates also have better structure designability.Therefore,in this review,we will review the research progress of F-containing iodates and address the effect of structure-directing properties of oxide-fluoride anions on the crystal structures of F-containing iodates.Since the valence of the central cations will greatly affect the distortions and configurations of the oxide-fluoride anion groups,these F-containing iodates will be classified and introduced according to the different valences of the central cations.展开更多
It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the s...It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.展开更多
A new organic/inorganic hybrid nonlinear optical (NLO) material was developed by the sol-gel process of an alkoxysilane dye with tetraethoxysilane. A NLO moiety based on 4-nitro-4 ' -hydroxy azobenzene was covalen...A new organic/inorganic hybrid nonlinear optical (NLO) material was developed by the sol-gel process of an alkoxysilane dye with tetraethoxysilane. A NLO moiety based on 4-nitro-4 ' -hydroxy azobenzene was covalently bonded to the triethoxysilane derivative, i.e, gamma -isocyanatopropyl triethoxysilane. The preparation process and properties of the sol-gel derived NLO polymer were studied and characterized by SEM, FTIR,H-1-NMR, UV-Vis, DSC and second harmonic generation (SHG) measurement. The results indicated that the chemical bonding of the chromophores to the inorganic SiO2 networks induces low dipole alignment relaxation and preferable orientational stability. The SHG measurements also showed that the bonded polymer film containing 75 wt% of the akoxysilane dye has a high electro-optic coefficient (r(33)) of 7.1 pm/V at 1.1 mum wavelength, and exhibit good SHG stability, the r(33) values can maintain about 92.7% of its initial value at room temperature for 90 days, and can maintain about 59.3% at 100 degreesC for 300 min.展开更多
A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phas...A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.展开更多
This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, ...This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, H-1 NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (beta) are calculated and compared with those or the analogues containing either benzene or thiophene as file conjugation bridge.展开更多
In the current investigation,L-proline cadmium chloride monohydrate（LPCC） single crystal is grown by a slow solvent evaporation technique to identify its credibility for nonlinear optical device applications.The con...In the current investigation,L-proline cadmium chloride monohydrate（LPCC） single crystal is grown by a slow solvent evaporation technique to identify its credibility for nonlinear optical device applications.The constituent elements of LPCC crystal are determined by the energy dispersive spectroscopic（EDS） technique.The single crystal x-ray diffraction technique is used to determine the structural dimensions of LPCC crystal.The UV-visible studies are carried out within a wavelength range of 200 nm–1100 nm to determine the optical transmittance of LPCC crystal.The linear optical parameters of LPCC crystal are evaluated using the transmittance data to discuss its importance for distinct optical devices.The Nd：YAG laser assisted Kurtz–Perry test is carried out to determine the enhancement in second harmonic generation efficiency of LPCC crystal with reference to KDP crystal.The Z-scan technique is employed to assess the third order nonlinear optical（TONLO） properties of LPCC crystal at 632.8 nm.The Z-scan data are utilized to evaluate the TONLO refraction,absorption and susceptibility of LPCC crystal.The color oriented luminescence behavior of LPCC crystal is investigated within a spectral range of 350 nm–700 nm.The dependence of dielectric constant and dielectric loss on temperature and frequency is evaluated through the dielectric measurement studies.展开更多
The new tetracarbonyl - chromium-triphenyl phosphine complex was synthesized and characterized using ultraviolet（UV）-visible,Fourier transform infrared（FTIR）,and nuclear magnetic resonance（NMR） techniques.The ch...The new tetracarbonyl - chromium-triphenyl phosphine complex was synthesized and characterized using ultraviolet（UV）-visible,Fourier transform infrared（FTIR）,and nuclear magnetic resonance（NMR） techniques.The characterization results confirm the molecular structure of the new complex.The z-scan measurements were done by diode laser[continuous wave（CW）]to estimate the nonlinear optical parameter（X^3）.The results led to calculate three parameters：the groundstate cross sections（σ_g）,the excited-state cross sections（σ_（ex））,and thermo-optic coefficient of the new complex.This study indicated that our complex is a suitable for photonic applications.展开更多
Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-...Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-2NH2-GNR lithium salts, especially cis lithium salts, display considerably large β0 values. The combination of NH2-substituting and cis Li-doping makes β0 greatly increased from 0（GNR） to 1.2×105―2.9×105 a.u.（cis-2Li- 2NH2-GNRs）. Our largest β0 value（2.9×105 a.u.） for cis-2Li-1,3-2NH2-AGNR is comparable to the record value of 1.7×105 a.u. for a long donor-acceptor polyene.展开更多
文摘we have synthesised a series of new optically nonlinear organic materials of cinnamylidene-acetophenone derivatives which have large nonl inear optical susceptibilities and short cut-off wavelengths.
基金Plan Project of Science and Technology of Guangzhou City (2002J1-C0061) The First Author: XI Hongxia(1968-)
文摘hydroxy-4-nitro azobenzene (NHA) and 4-amino-4-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) materials containing NHA and DO3 were synthesized by Sol-Gel process. The preparation and properties of two NLO materials were studied and characterized by FTIR, 1H-NMR, UV-VIS, SEM, DSC and SHG measurements. The results show that the maximum doping amounts of NHA and DO3 in two doped hybrid NLO materials are 7.2(wt)% and 11.3(wt)% respectively, and the corresponding second-order NLO coefficients (d33 values) are 2.91×10 8esu and 6.14×10 8esu. Two doped NLO materials have relatively good RT stability, after 90 days at RT the d33 values can maintain about 85% of their initial values, but after 10h at 100℃ can only maintain about 50% of their initial values. In this report, the reasons for high-temperature instability of doped materials were discussed, and the possible improvements were also suggested.
基金supported by the Natural Science Foundation of the Xinjiang Uygur Autonomous Region(2023D01A04 and 2022D01B206)the Shanghai Cooperation Organization Science and Technology Partnership Program(2023E01001)+1 种基金the National Natural Science Foundation of China(22335007,22361132544,62305382,and 52302011)the support from Tianchi Doctor Plan of Xinjiang Uygur Autonomous Region。
文摘The simultaneous achievement of wide band gap and strong nonlinear optical(NLO)effect poses a challenging task in the development of infrared(IR)NLO materials.The coupling strategy of polyhedral building blocks has been demonstrated to be one of the effective approaches for constructing superior optical materials with well-balanced performance.Here,a new family of IR NLO materials A^(I)_(2)Mg_(3)Ga_(12)S_(22)(AI=K,Rb)that first contain[MgS_(6)]octahedra and T2-type supertetrahedra was designed and synthesized.K_(2)Mg_(3)Ga_(12)S_(22) exhibits a wide band gap of 3.34 eV,and a moderate second-harmonic generation response intensity of 0.4 times that of AgGaS2 under 2µm Q-switched laser radiation.Furthermore,the birefringence of K_(2)Mg_(3)Ga_(12)S_(22) is calculated to be 0.028@1064 nm,resulting in favorable phase-matching behavior in IR region.These characteristics suggest that K_(2)Mg_(3)Ga_(12)S_(22) could be a promising material for nonlinear frequency conversion applications and it provides new ideas into the design of novel compounds with outstanding IR NLO performances.
基金support by the Key Research and Development Program of Zhejiang Province(2023C01102,2023C01208,2022C01208)。
文摘To rationalize the design of D-π-A type organic small-molecule nonlinear optical materials,a theory guided machine learning framework is constructed.Such an approach is based on the recognition that the optical property of the molecule is predictable upon accumulating the contribution of each component,which is in line with the concept of group contribution method in thermodynamics.To realize this,a Lewis-mode group contribution method(LGC)has been developed in this work,which is combined with the multistage Bayesian neural network and the evolutionary algorithm to constitute an interactive framework(LGC-msBNN-EA).Thus,different optical properties of molecules are afforded accurately and efficientlyby using only a small data set for training.Moreover,by employing the EA model designed specifically for LGC,structural search is well achievable.The origins of the satisfying performance of the framework are discussed in detail.Considering that such a framework combines chemical principles and data-driven tools,most likely,it will be proven to be rational and efficient to complete mission regarding structure design in related fields.
基金supported by the Guangzhou Municipal Science and Technology Project(No.202102010426)the National Natural Science Foundation of China(Nos.21805049 and 22074025)Engineering Research Centre of Photonic Design Software,Ministry of Education,China(No.62175267).
文摘How to obtain organic electro-optic materials with large electro-optic coefficients,high glass transition temperature,and good optical transparency remains a challenge in this field.To solve this problem,we introduce groups that can undergo Huisgen cycloaddition reactions into the donor and electron bridge of chromophores with large hyperpolarizability using tetrahydroquinoline as the donor.Binary cross-linkable chromophores TLD1-2 with CF_(3)-TCF as the acceptor and chromophores TLD3-4 with 5Fph-TCF as the acceptor were synthesized.After poling and crosslinking,the T_(g)of TLD1/TLD2 and TLD3/TLD4 were raised to 152 and 174°C,respectively.The electro-optical coefficients of chromophores TLD1/TLD2 and TLD3/TLD4 were as high as 312 pm/V and 287 pm/V,respectively.The long-term alignment stability test showed that after being left at 85℃ for 500 h,the cross-linked film TLD3/TLD4 can still maintain more than 98%of the original electro-optical coefficient value,which is higher than that of TLD1/TLD2(93%).The chromophore TLD3-4 exhibited much blue-shifted maximum absorption wavelengths(~40 nm)compared to TLD1-2 which was beneficial for reducing optical loss in the device.The combination of high electro-optic coefficient,strong stability,and excellent optical transparency makes the TLD series of binary cross-linked materials very promising for practical high-performance electro-optic devices.
基金supported by Tianshan Innovation Team Program (2018D14001)the National Natural Science Foundation of China (51922014 and 11774414)+2 种基金Shanghai Cooperation Organization Science and Technology Partnership Program (2017E01013)Xinjiang Program of Introducing High-Level Talents, Fujian Institute of Innovation, Chinese Academy of Sciences (FJCXY18010202)the Western Light Foundation of CAS (2017-XBQNXZ-B-006 and 2016QNXZ-B-9)
文摘Exploration of new infrared(IR) nonlinear optical(NLO) materials is still in urgency owing to the indispensable roles in optoelectronic devices, resource exploration, and long-distance laser communication. The formidable challenge is to balance the contradiction between wide band gaps and large second harmonic generation(SHG) effects in IR NLO materials. In the present work, we proposed new kinds of NLO active units, d^0 transition metal fluorooxofunctional groups for designing mid-IR NLO materials. By studying a series of d^0 transition metal oxyfluorides(TMOFs),the influences of fluorooxo-functional groups with different d^0 configuration cations on the band gap and SHG responses were explored. The results reveal that the fluorooxo-functional groups with different d^0 configuration cations can enlarge band gaps in mid-IR NLO materials. The first-principles calculations demonstrate that the nine alkali/alkaline earth metals d^0 TMOFs exhibit wide band gaps(all the band gaps >3.0 e V), large birefringence Δn(> 0.07), and two W/Mo TMOFs also exhibit large SHG responses. Moreover, by comparing with other fluorooxo-functional groups, it is found that introducing fluorine into building units is an effective way to enhance optical performance. These d^0 TMOFs with superior fluorooxo-functional groups represent a new exploration family of the mid-IR region, which sheds light on the design of mid-IR NLO materials possessing large band gap.
基金supported by the West Light Foundation of the CAS(2016-YJRC-2 and 2015 XBQN-B-11)the National Natural Science Foundation of China(51602341 and 91622107)+2 种基金the Natural Science Foundation of Xinjiang(2016D01B061)Tianshan Innovation Team Program(2018D14001)Key research project of Frontier Science of CAS(QYZDB-SSW-JSC049)
文摘Three new complex borate compounds K7CaBi2B15O30,K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space group R32,while K7BaBi2B15O30 crystallizes in the noncentrosymmetric orthorhombic polar space group Pca21.All of the title compounds have similar three-dimensional crystal structures,which are composed of isolated B5 O10 groups and LaO6 or BiO6 octahedra,and K^+,Ca^2+,and Ba^2+cations fill into the cavities to keep charge balance.Based on our research,in the system of K7 MIIRE2 B15O30(MII=Ca,Sr,Ba,Zn,Cd,Pb,K/RE0.5;RE=Sc,Y,La,Gd,Lu,Bi),K7BaBi2B15O30 is unique and crystallizes in a different space group,which enriches the structural chemistry of borate.Detailed structural analyses indicate that the structural variation is due to the difference in size and coordination number of the alkaline-earth metal cations.Besides,UV-Vis-NIR spectroscopy analysis and the second-harmonic generation(SHG)measurement on the powder samples show that K7CaBi2B15O30 exhibits a UV cutoff edge(about 282 nm)and a moderate SHG response(about 0.6×KDP).In addition,thermal analysis and infrared spectroscopy were also presented.To better understand the structure-property relationships of the title compounds,the first-principles calculations have been performed.
文摘The nonlinear optical （NLO） and optical limiting （OL） properties of three new structures of organic NLO vip host Poly（N-vinylcarbozole）/disperse orange 3 （PVK/DO3）, PVK/disperse orange 13 （PVK/DO13）. and PVK/disperse orange 25 （PVK/DO25） as a solution at different concentrations and as a thin-film sample are studied using continuous wave z-scan system at 532 nm. The open-aperture z-scan data of the NLO materials in the solution and thin-film samples displayed two-photon and saturable absorptions, respectively. The PVK/DO13 exhibites the largest and best values of the nonlinearities, such as n2, β, X（3） compared with those of PVK/DO3 and PVK/DO25. This nonlinearity increases as the concentration increases. Tile results indicate that these NLO materials are good candidates for optical switching and OL devices.
基金supported by the National Natural Science Foundation of China (20701023 & 51102138)the Natural Science Foundation of Shandong Province, China (BS2010NJ004 &2009ZRB019KH)
文摘Employing unsymmetrical 2-mercapto-5-methyl-1,3,4-thiadiazole and 2,2′-bipyridine as mixed ligands, a new low-dimensional coordination polymer [Zn(MMTA) 2 (2,2′-bipy)] n (MMTA = 2-mercapto-5-methyl-1,3,4-thiadiazole, 2,2′-bipy = 2,2′-bipyridine), has been synthesized under solvothermal condition and characterized by single crystal X-ray diffraction. This compound crys- tallizes in the noncentrosymmetric space group Cc, with cell parameters: a = 8.291(4) , b = 15.483(9) , c = 15.620(6) , = 96.00(5)°, V = 1994.1(2) 3 , and Z = 4. The mixed ligands link the zinc center into a mononuclear unit, which is futher linked by weak C-H···N and C-H···S hydrogen bonds into a three-dimensional noncentrosymmetric framework. The compound exhibits intense photoluminescence and distinct NLO properties at room temperature. The intensity of the green light produced by the powder sample of the compound is about 3.2 times that produced by KDP powder. On the basis of the results of TG analysis, the structure is thermally stable up to ～260 °C.
基金Supported by National Natural Science Foundation of China(21971171,21875146)。
文摘Ultraviolet(UV)nonlinear optical(NLO)crystal materials are hailed as the"chip"of the optoelectronic industry for they play a unique and crucial role in many newly developed scientific and technological applications.At present,due to the relatively single frequency doubling gene types of traditional NLO materials,the service performance of UV NLO materials is fundamentally restricted.Therefore,there is an urgent need to develop new synthesis methods,search for novel functional groups,expand new UV NLO materials systems,screen new high-performance crystals,and then break through performance bottlenecks.Herein,we review the recent progresses on UV NLO crystal materials.Furthermore,we prospect that these recently developed approaches will continuously extend their advantages in developing superior UV NLO materials in the near future.
基金supported by the National Natural Science Foundation of China(21921001,22075283,92161125,U21A20508)the Youth Innovation Promotion Association of Chinese Academy of Sciences of China(2021300)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ108,2021ZR205).
文摘Nonlinear optical(NLO)material are of great importance in converting the frequency to extend the laser spectrum in mid-and far-infrared(IR)regions where lasers operate poorly or are unavailable.However,the contradiction between large second-harmonic generation(SHG)intensity and wide band gap(E_(g))is a long-standing problem for IR NLO materials.To address the issue,metal chalcogenides have been successfully synthesized and developed excellent optical properties in the past few decades.As a newly discovered category of chalcogenides,salt-inclusion chalcogenides with distinctive structures and brilliant performances have been placed great expecta-tions to be a novel problem-solving.In this review,52 compounds in this thriving family are categorized via dimensions of host and vip parts,further discussing the relationships between their structures and NLO properties,as well as future perspectives of this family.
基金financial support from the Guangdong Innovative Research Team Program of China (201101C0105067115)DSTA Singapore (Project DSTA-NUS-DIRP/9010100347)National Research Foundation Singapore (R398-001-062-281)
文摘We report a simple solution-processed method for the fabrication of low-cost,flexible optical limiting materials based on graphene oxide(GO) impregnated polyvinyl alcohol(PVA) sheets.Such GO–PVA composite sheets display highly efficient broadband optical limiting activities for femtosecond laser pulses at 400,800,and 1400 nm with very low limiting thresholds.Femtosecond pump–probe measurement results revealed that nonlinear absorption played an important role for the observed optical limiting activities.High flexibility and efficient optical limiting activities of these materials allow these composite sheets to be attached to nonplanar optical sensors in order to protect them from light-induced damage.
基金supported by the National Natural Science Foundation of China,China(Grant Nos.22071179,51902224,51972230,52172006,51890864,51890865)Natural Science Foundation of Tianjin,China(Grant Nos.20JCJQJC00060,21JCJQJC00090).
文摘Metal iodates containing I(Ⅴ)with lone electron pairs in an asymmetric coordination geometry exhibit excellent second-harmonic generation(SHG)responses,wide transmission range and large band gaps.During the past ten years,metal iodates have been widely studied,and introducing large electronegative fluorine atoms into metal iodates has also attracted much attention.These F-containing iodates are different from pure iodates in terms of composition,symmetry and transmittance.Especially because oxide-fluoride heterolepic anion groups can exhibit interesting structure-directing properties,e.g.trans-and cis-directing properties,these F-containing iodates also have better structure designability.Therefore,in this review,we will review the research progress of F-containing iodates and address the effect of structure-directing properties of oxide-fluoride anions on the crystal structures of F-containing iodates.Since the valence of the central cations will greatly affect the distortions and configurations of the oxide-fluoride anion groups,these F-containing iodates will be classified and introduced according to the different valences of the central cations.
基金the Natural Science Foundation of China(No.22105218).
文摘It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.
基金This work was supported by the Postdoctoral Science Foundation of Guangdong Province (No. 9644) and the Natural Science Fund of Guangdong Province(No. 990629).
文摘A new organic/inorganic hybrid nonlinear optical (NLO) material was developed by the sol-gel process of an alkoxysilane dye with tetraethoxysilane. A NLO moiety based on 4-nitro-4 ' -hydroxy azobenzene was covalently bonded to the triethoxysilane derivative, i.e, gamma -isocyanatopropyl triethoxysilane. The preparation process and properties of the sol-gel derived NLO polymer were studied and characterized by SEM, FTIR,H-1-NMR, UV-Vis, DSC and second harmonic generation (SHG) measurement. The results indicated that the chemical bonding of the chromophores to the inorganic SiO2 networks induces low dipole alignment relaxation and preferable orientational stability. The SHG measurements also showed that the bonded polymer film containing 75 wt% of the akoxysilane dye has a high electro-optic coefficient (r(33)) of 7.1 pm/V at 1.1 mum wavelength, and exhibit good SHG stability, the r(33) values can maintain about 92.7% of its initial value at room temperature for 90 days, and can maintain about 59.3% at 100 degreesC for 300 min.
文摘A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.
基金the National Natural Science Foundation of China(No.29774018) a grant from the National Key Fundamental Research Program of China.
文摘This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, H-1 NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (beta) are calculated and compared with those or the analogues containing either benzene or thiophene as file conjugation bridge.
基金UGC,New Delhi,India for awarding Maulana Azad National Fellowship(Grant No.F1-17.1/2015-16/MANF-2015-17-MAH-68193)RCAMSKing Khalid University,Saudi Arabia for support
文摘In the current investigation,L-proline cadmium chloride monohydrate（LPCC） single crystal is grown by a slow solvent evaporation technique to identify its credibility for nonlinear optical device applications.The constituent elements of LPCC crystal are determined by the energy dispersive spectroscopic（EDS） technique.The single crystal x-ray diffraction technique is used to determine the structural dimensions of LPCC crystal.The UV-visible studies are carried out within a wavelength range of 200 nm–1100 nm to determine the optical transmittance of LPCC crystal.The linear optical parameters of LPCC crystal are evaluated using the transmittance data to discuss its importance for distinct optical devices.The Nd：YAG laser assisted Kurtz–Perry test is carried out to determine the enhancement in second harmonic generation efficiency of LPCC crystal with reference to KDP crystal.The Z-scan technique is employed to assess the third order nonlinear optical（TONLO） properties of LPCC crystal at 632.8 nm.The Z-scan data are utilized to evaluate the TONLO refraction,absorption and susceptibility of LPCC crystal.The color oriented luminescence behavior of LPCC crystal is investigated within a spectral range of 350 nm–700 nm.The dependence of dielectric constant and dielectric loss on temperature and frequency is evaluated through the dielectric measurement studies.
文摘The new tetracarbonyl - chromium-triphenyl phosphine complex was synthesized and characterized using ultraviolet（UV）-visible,Fourier transform infrared（FTIR）,and nuclear magnetic resonance（NMR） techniques.The characterization results confirm the molecular structure of the new complex.The z-scan measurements were done by diode laser[continuous wave（CW）]to estimate the nonlinear optical parameter（X^3）.The results led to calculate three parameters：the groundstate cross sections（σ_g）,the excited-state cross sections（σ_（ex））,and thermo-optic coefficient of the new complex.This study indicated that our complex is a suitable for photonic applications.
基金Supported by the National Natural Science Foundation of China(Nos.20773046, 20773048 and 21073075)
文摘Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-2NH2-GNR lithium salts, especially cis lithium salts, display considerably large β0 values. The combination of NH2-substituting and cis Li-doping makes β0 greatly increased from 0（GNR） to 1.2×105―2.9×105 a.u.（cis-2Li- 2NH2-GNRs）. Our largest β0 value（2.9×105 a.u.） for cis-2Li-1,3-2NH2-AGNR is comparable to the record value of 1.7×105 a.u. for a long donor-acceptor polyene.
