NEW ORGANIC NONLINEAR OPTICAL MATERIALS OF CINNAMYLIDENE-ACETOPHENONE DERIVATIVES

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.

SYNTHESIS AND CHARACTERIZATION OF NOVEL SOL-GEL DOPED ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL MATERIALS

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.

SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

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.

Group Contribution Method Supervised Neural Network for Precise Design of Organic Nonlinear Optical Materials

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.

SYNTHESIS AND OPTICAL PROPERTIES OF A NOVEL ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL POLYMER VIA SOL-GEL PROCESS

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.

Synthesis and Nonlinear Optical Property of a Series of New Chromophores Containing Furan Ring as the Only Conjugation Bridge

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.

Linear and nonlinear optical analysis on semiorganic-proline cadmium chloride single crystal

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.

Optical nonlinearities of tetracarbonyl-chromium triphenyl phosphine complex

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.

Lithium Salt of NH_2-substituted Graphene Nanoribbon with Twofold Donor-acceptor Framework: Large Nonlinear Optical Property

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.

The compatibly large nonlinear optical effect and high laser-induced damage threshold in a thiophosphate CsInP_(2)S_(7)constructed with[P_(2)S_(7)]^(4-)and[InS_(6)]^(9-)

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.

Recent advances in F-containing iodate nonlinear optical materials

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.

Salt-inclusion chalcogenides:Double functional moieties design strategy toward excellent nonlinear optical materials

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 guest parts,further discussing the relationships between their structures and NLO properties,as well as future perspectives of this family.

MoS_2 saturable absorber prepared by chemical vapor deposition method for nonlinear control in Q-switching fiber laser

Due to the remarkable carrier mobility and nonlinear characteristic, MoS2 is considered to be a powerful competitor as an effective optical modulated material in fiber lasers. In this paper, the MoS2 films are prepared by the chemical vapor deposition method to guarantee the high quality of the crystal lattice and uniform thickness. The transfer of the films to microfiber and the operation of gold plated films ensure there is no heat-resistant damage and anti-oxidation. The modulation depth of the prepared integrated microfiber-MoS2 saturable absorber is 11.07%. When the microfiber-MoS2 saturable absorber is used as a light modulator in the Q-switching fiber laser, the stable pulse train with a pulse duration of 888 ns at 1530.9 nm is obtained. The ultimate output power and pulse energy of output pulses are 18.8 mW and 88 nJ, respectively. The signal-to-noise ratio up to 60 dB indicates the good stability of the laser. This work demonstrates that the MoS2 saturable absorber prepared by the chemical vapor deposition method can serve as an effective nonlinear control device for the Q-switching fiber laser.

Synthesis of AgGa_(1-x)In_(x)Se_(2) Polycrystalline Materials

AgGa_(1-x)In_(x)Se_(2)polycrystals were synthesized by the method of mechanical oscillation and temperature oscillation.X-ray diffraction spectra of polycrystal powder are conformable with the JCPDS cards.Lattice constants a and c calculated from the XRD were found to obey Vegard's law.The melting point of AgGa_(0.8)In_(0.2)Se_(2)obtained by means of differential scanning calorimetry(DSC)is 796.53℃.The DSC curve also show that there are no other transformation points below the melting point.The results indicate that polycrystalline materials synthesized by the method mentioned above are high-quality and can be used to grow single crystals by the vertical Bridgman technology.

Optical properties and applications of SnS_(2) SAs with different thickness

Q-switched lasers have occupied important roles in industrial applications such as laser marking,engraving,welding,and cutting due to their advantages in high pulse energy.Here,SnS_(2)-based Q-switched lasers are implemented.Consid-ering that SnS_(2) inherits the thickness sensitive optical characteristics of TMD,three kinds of SnS2 with different thick-ness are characterized in terms of nonlinearity and used to realize the Q-switched pulses under consistent implementa-tion conditions for comparison tests.According to the results,the influence of thickness variation on the nonlinear per-formance of saturable absorber,such as modulation depth and absorption intensity,and the influence on the correspond-ing laser are analyzed.In addition,compared with other traditional saturable absorbers,the advantage of SnS_(2) in realiz-ing ultrashort pulses is also noticed.Our work explores the thickness-dependent nonlinear optical properties of SnS_(2),and the rules found is of great reference value for the establishment of target lasers.

Optical and Electrical Properties of Polyimide Thin Films Doped-Cu-phthalocyanine Polymerized by Vapor Phase Deposition

Using Cu-phthalocyanine（CuPc）,4,4’-diaminodiphenyl ether and pyromellitic dianhydride as monomer materials, polyimide（PI） thin films doped-CuPc have been prepared onto glass substrate by vapor phase co-deposition polymerization under a vacuum of 2×10-3Pa and thermal curing of polyamic acid film in at temperature of 150-200℃ for 60min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition rates of the three monomers. IR spectrum identifies the designed chemical structure of the polymer. The absorption of polyimide doped-CuPc is very intense in vis-range and near-infrared by UV-Vis spectrum. And, the PI films doped-CuPc polymerized by vapor phase deposition have uniformity, fine thermal stability and good nonlinear optical properties, and the third-order optical nonlinear susceptibility χ（3） with degenerate four-wave mixing can be 1.984×10-9ESU.

Optical and Electrical Properties of Polyimide Thin Films Grown by Vapor Deposition Polymerization

Using pyromellitic dianhydride (PMDA) and 4,4’ diaminodiphenyl ether (ODA) as monomer materials, polyimide thin films have been prepared onto glass substrate by vapor deposition polymerization under a vacuum of 2.666×10 -3 Pa and thermal curing of polyamic acid film in a vacuum at temperature of 150～200 ℃ for 60 min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition ratio of the two monomers. The composition, the structure and properties of the polyimide films are investigated with IR spectrum, XRD, and SEM methods. The results show that the polyimide films by vapor deposition polymerization have good electrical properties and thermal stability. Therefore, the vapor deposition polymerization process is considered as a possible method of polymerization for other polymers.

Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d^0 transition metal oxyfluorides

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.

Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30（M= Ca and Ba, RE= La and Bi）

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.

Nonlinear optical and optical limiting properties of new structures of organic nonlinear optical materials for photonic applications

The nonlinear optical （NLO） and optical limiting （OL） properties of three new structures of organic NLO guest 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.