Recent advances in bionic optical materials(BOMs)are systematically reviewed,emphasizing bioinspired strategies derived from natural models such as plant epidermis,aquatic organisms,avian plumage,and insect photonic a...Recent advances in bionic optical materials(BOMs)are systematically reviewed,emphasizing bioinspired strategies derived from natural models such as plant epidermis,aquatic organisms,avian plumage,and insect photonic architectures(e.g.,butterfly wings and inverse opal structures).These biological systems exhibit so-phisticated light manipulation mechanisms,including absorption,scattering,and structural coloration,which have guided the design of novel extinction materials with tunable optical properties.By mimicking hierarchical structures and dynamic light-regulation principles,researchers have developed BOMs exhibiting exceptional broadband extinction performance.Notably,applications in optical sensing and imaging systems are critically discussed,highlighting their role in enhancing camera sensitivity and adaptive optical sensor design.Furthermore,this review identifies emerging trends in nanofabrication,machine learning-assisted optimization,and biohybrid material systems.The integration of cross-disciplinary approaches is projected to accelerate the development of multifunctional BOMs,paving the way for breakthroughs in adaptive optics,environmental monitoring,and intelligent photonic devices.In the future,the integration of BOMs and distributed fiber optic sensing technology is expected to realize the whole-life optical monitoring of pile foundation structural health,and promote the development of geotechnical engineering in the direction of intelligence and high precision.展开更多
A theoretical model of relationship between subsurface damage and surface roughness was established to realize rapid and non-destructive measurement of subsurface damage of ground optical materials.Postulated conditio...A theoretical model of relationship between subsurface damage and surface roughness was established to realize rapid and non-destructive measurement of subsurface damage of ground optical materials.Postulated condition of the model was that subsurface damage depth and peak-to-valley surface roughness are equal to depth of radial and lateral cracks in brittle surface induced by small-radius(radius≤200 μm)spherical indenter,respectively.And contribution of elastic stress field to the radial cracks propagation was also considered in the loading cycle.Subsurface damage depth of ground BK7 glasses was measured by magnetorheological finishing spot technique to validate theoretical ratio of subsurface damage to surface roughness.The results show that the ratio is directly proportional to load of abrasive grains and hardness of optical materials,while inversely proportional to granularity of abrasive grains and fracture toughness of optical materials.Moreover,the influence of the load and fracture toughness on the ratio is more significant than the granularity and hardness,respectively.The measured ratios of 80 grit and 120 grit fixed abrasive grinding of BK7 glasses are 5.8 and 5.4,respectively.展开更多
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
Bluelightning Optics Co.,Ltd.(BOC)；The Featured of BOC's Nd:YLF:；Juhua Group Xinghua Crystal Materials Factory；Fujian Castech Crystals, Inc. (CASTECH)；Shanghai Fanguang Industry and Commerce Co.
In the 5 G era,the demand for high-capacity and fast fiber-optic communication underscores the importance of inorganic optical materials with high electro-optical(EO)coefficients,rapid responses,and stability for effi...In the 5 G era,the demand for high-capacity and fast fiber-optic communication underscores the importance of inorganic optical materials with high electro-optical(EO)coefficients,rapid responses,and stability for efficient electro-optical modulators.The exploration of novel EO materials and their applications remains in the early stages.At present,research mainly focuses on the performance of EO materials and devices.However,the EO coefficients of different preparation methods for the same material and different materials vary significantly.Currently,a crucial gap lies in understanding the link between the EO effect and ferroelectric polarization,hindering advancements in ferroelectric material optimization.This article offers a comprehensive insight into the EO effect,initially discussing ferroelectric polarization and its relationship to the phenomenon.It then reviews standard inorganic ABO_(3) metal oxide ferroelectric ceramics and thin films,followed by an examination of emerging ferroelectrics such as HfO_(2)-based polymorph ferroelectrics and ZnO/AIN-based materials.The article concludes by addressing the challenges in investigating ferroelectric EO mechanisms and provides an outlook on the future of EO material research,including a review of the latest developments in EO effect mechanisms and their optimization for light modulation,as well as an exploration of potential areas for high-performance EO materials research.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
Finding crystals with high birefringence(Δn),especially in deep-ultraviolet(DUV)regions,is important for developing polarization devices such as optical fiber sensors.Such materials are usually discovered using exper...Finding crystals with high birefringence(Δn),especially in deep-ultraviolet(DUV)regions,is important for developing polarization devices such as optical fiber sensors.Such materials are usually discovered using experimental techniques,which are costly and inefficient for a large-scale screening.Herein,we collected a database of crystal structures and their optical properties and trained atomistic line graph neural network to predict theirΔn.To estimate the level of confidence of the trained model on new data,D-optimality criterion was implemented.Using trained graph neural network,we searched for novel materials with highΔn in the Materials Project database and discovered two new DUV birefringent candidates:NaYCO_(3)F_(2) and SClO_(2)F,with highΔn values of 0.202 and 0.101 at 1064 nm,respectively.Further analysis reveals that strongly anisotropic units with various anions andπ-conjugated planar groups are beneficial for highΔn.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
Diketopyrrolopyrrole(DPP)and related derivatives have drawn great attention due to their applications in organic optical/electronic materials.Progress in these materials is associated with developments in the synthese...Diketopyrrolopyrrole(DPP)and related derivatives have drawn great attention due to their applications in organic optical/electronic materials.Progress in these materials is associated with developments in the syntheses of the DPP family.Chemical modification of DPP at nitrogen atom,including N-alkylation and N-arylation,is an effective strategy to improve its physical and chemical properties,such as solubility,optical and semiconducting properties.However,N-arylation of DPPs remains challenging compared to the easily accessible N-alkylation.Herein,the synthesis of N-aryl DPP derivatives and correlatedπ-expanded DPPs are summarized,and their optical/electronic properties are introduced.The future perspectives of N-aryl DPP derivatives are also discussed.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
基金the financial support provided by Graduate Scientific Research and Innovation Foundation of Chongqing,China(CYB22007,CYS22005)Projects(No.2020CDJXZ001)supported by the Fundamental Research Funds for the Central Universities+1 种基金the Technology Innovation and Application Development Special Project of Chongqing(Z20211350 and z20211351)Scientific Research Project of Chongqing Ecological Environment Bureau(No.CQEE2022-STHBZZ118).
文摘Recent advances in bionic optical materials(BOMs)are systematically reviewed,emphasizing bioinspired strategies derived from natural models such as plant epidermis,aquatic organisms,avian plumage,and insect photonic architectures(e.g.,butterfly wings and inverse opal structures).These biological systems exhibit so-phisticated light manipulation mechanisms,including absorption,scattering,and structural coloration,which have guided the design of novel extinction materials with tunable optical properties.By mimicking hierarchical structures and dynamic light-regulation principles,researchers have developed BOMs exhibiting exceptional broadband extinction performance.Notably,applications in optical sensing and imaging systems are critically discussed,highlighting their role in enhancing camera sensitivity and adaptive optical sensor design.Furthermore,this review identifies emerging trends in nanofabrication,machine learning-assisted optimization,and biohybrid material systems.The integration of cross-disciplinary approaches is projected to accelerate the development of multifunctional BOMs,paving the way for breakthroughs in adaptive optics,environmental monitoring,and intelligent photonic devices.In the future,the integration of BOMs and distributed fiber optic sensing technology is expected to realize the whole-life optical monitoring of pile foundation structural health,and promote the development of geotechnical engineering in the direction of intelligence and high precision.
基金Project(50375156) supported by the National Natural Science Foundation of China
文摘A theoretical model of relationship between subsurface damage and surface roughness was established to realize rapid and non-destructive measurement of subsurface damage of ground optical materials.Postulated condition of the model was that subsurface damage depth and peak-to-valley surface roughness are equal to depth of radial and lateral cracks in brittle surface induced by small-radius(radius≤200 μm)spherical indenter,respectively.And contribution of elastic stress field to the radial cracks propagation was also considered in the loading cycle.Subsurface damage depth of ground BK7 glasses was measured by magnetorheological finishing spot technique to validate theoretical ratio of subsurface damage to surface roughness.The results show that the ratio is directly proportional to load of abrasive grains and hardness of optical materials,while inversely proportional to granularity of abrasive grains and fracture toughness of optical materials.Moreover,the influence of the load and fracture toughness on the ratio is more significant than the granularity and hardness,respectively.The measured ratios of 80 grit and 120 grit fixed abrasive grinding of BK7 glasses are 5.8 and 5.4,respectively.
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.
文摘Bluelightning Optics Co.,Ltd.(BOC)；The Featured of BOC's Nd:YLF:；Juhua Group Xinghua Crystal Materials Factory；Fujian Castech Crystals, Inc. (CASTECH)；Shanghai Fanguang Industry and Commerce Co.
基金the support of the Natural Science Foundation of China(52202134)the National Key Research and Development Program of China(2021YFA1202100)the Hubei Nature Science Foundation(2022CFB595).
文摘In the 5 G era,the demand for high-capacity and fast fiber-optic communication underscores the importance of inorganic optical materials with high electro-optical(EO)coefficients,rapid responses,and stability for efficient electro-optical modulators.The exploration of novel EO materials and their applications remains in the early stages.At present,research mainly focuses on the performance of EO materials and devices.However,the EO coefficients of different preparation methods for the same material and different materials vary significantly.Currently,a crucial gap lies in understanding the link between the EO effect and ferroelectric polarization,hindering advancements in ferroelectric material optimization.This article offers a comprehensive insight into the EO effect,initially discussing ferroelectric polarization and its relationship to the phenomenon.It then reviews standard inorganic ABO_(3) metal oxide ferroelectric ceramics and thin films,followed by an examination of emerging ferroelectrics such as HfO_(2)-based polymorph ferroelectrics and ZnO/AIN-based materials.The article concludes by addressing the challenges in investigating ferroelectric EO mechanisms and provides an outlook on the future of EO material research,including a review of the latest developments in EO effect mechanisms and their optimization for light modulation,as well as an exploration of potential areas for high-performance EO materials research.
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supported by the National Key Research and Development Program of China(2021YFB3601501)the Key Research Program of Frontier Sciences,Chinese Academy of Scineces(CAS,ZDBSLY-SLH035)+7 种基金the National Natural Science Foundation of China(22193044,61835014,and 51972336)West Light Foundation of CAS(2019-YDYLTD002)the Natural Science Foundation of Xinjiang(2021D01E05)CAS Project for Young Scientists in Basic Research(YSBR-024)Xinjiang Major Science and Technology Project(2021A01001)CAS President’s International Fellowship Initiative(PIFI,2020PM0046)Tianshan Basic Research Talents(2022TSYCJU0001)Kruglov IA and Bereznikova LA thank the Ministry of Science and Higher Education of the Russian Federation(FSMG2021-0005)。
文摘Finding crystals with high birefringence(Δn),especially in deep-ultraviolet(DUV)regions,is important for developing polarization devices such as optical fiber sensors.Such materials are usually discovered using experimental techniques,which are costly and inefficient for a large-scale screening.Herein,we collected a database of crystal structures and their optical properties and trained atomistic line graph neural network to predict theirΔn.To estimate the level of confidence of the trained model on new data,D-optimality criterion was implemented.Using trained graph neural network,we searched for novel materials with highΔn in the Materials Project database and discovered two new DUV birefringent candidates:NaYCO_(3)F_(2) and SClO_(2)F,with highΔn values of 0.202 and 0.101 at 1064 nm,respectively.Further analysis reveals that strongly anisotropic units with various anions andπ-conjugated planar groups are beneficial for highΔn.
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the financial support from National Natural Science Foundation of China(NSFC,Nos.22175081 and 21833005)Beijing National Laboratory for Molecular Sciences(No.BNLM202010)+1 种基金State Key Laboratory of Physical Chemistry of Solid Surfaces(No.202108)Guangdong Provincial Key Laboratory of Catalysis(No.20210701)。
文摘Diketopyrrolopyrrole(DPP)and related derivatives have drawn great attention due to their applications in organic optical/electronic materials.Progress in these materials is associated with developments in the syntheses of the DPP family.Chemical modification of DPP at nitrogen atom,including N-alkylation and N-arylation,is an effective strategy to improve its physical and chemical properties,such as solubility,optical and semiconducting properties.However,N-arylation of DPPs remains challenging compared to the easily accessible N-alkylation.Herein,the synthesis of N-aryl DPP derivatives and correlatedπ-expanded DPPs are summarized,and their optical/electronic properties are introduced.The future perspectives of N-aryl DPP derivatives are also discussed.
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.
