Organic materials for nonlinear optics

This review discusses nonlinear optical (NLO) polymeric materials. As an example of a second-order NLO material, a novel copolymer with a diazo dye attached is investigated. The second-order NLO coefficient χ⁽²⁾ of the copolymer reaches 1.0 × 10^?6 esu, which is 7 times larger than that of LiNbO₃. A third-order NLO coefficient χ⁽³⁾ larger than 10^?10 esu is obtained for polymers where NLO dyes are introduced into the polymer backbone. The optical transmission loss of these polymers is revealed to be around 2 dB/cm. As these polymers can be formed into channel waveguides using the photo-bleaching technique, they show promise for use in NLO devices because of their processability, transparency and large optical nonlinearity.     

Halide Perovskites for Nonlinear Optics

Halide perovskites provide an ideal platform for engineering highly promising semiconductor materials for a wide range of applications in optoelectronic devices, such as photovoltaics, light-emitting diodes, photodetectors, and lasers. More recently, increasing research efforts have been directed toward the nonlinear optical properties of halide perovskites because of their unique chemical and electronic properties, which are of crucial importance for advancing their applications in next-generation photonic devices. Here, the current state of the art in the field of nonlinear optics (NLO) in halide perovskite materials is reviewed. Halide perovskites are categorized into hybrid organic/inorganic and pure inorganic ones, and their second-, third-, and higher-order NLO properties are summarized. The performance of halide perovskite materials in NLO devices such as upconversion lasers and ultrafast laser modulators is analyzed. Several potential perspectives and research directions of these promising materials for nonlinear optics are presented.     

Solvent effect on the third order optical nonlinearity and optical limiting ability of betanin natural dye extracted from red beet root

We report on the solvent effect on the third order optical nonlinearity of betanin natural dye extracted from red beet root and their third order nonlinear optical (NLO) properties have been studied using a Q-switched Nd:YAG laser at 532 nm. The third order nonlinearity of these samples are dominated by nonlinear absorption, which leads to strong optical limiting and their strength is influenced by the solvent used, suggesting that betanin natural dyes are promising candidate for the development of photonic nonlinear optic devices.     

Relaxation behavior and nonlinear properties of thermally stable polymers based on glycidyl derivatives of quercetin

Cross-linked polymers on the basis of di-, tri and tetraglycidyl ethers of quercetin (3,3′,4′,5,7-pentahydroxyflavone) were synthesized, and then, poled in electrical field of corona discharge. Investigations of structural, thermal and optical parameters of the polymer films were carried out. It was found that the polymers obtained from di- and triglycidyl quercetin ethers had high values of macroscopic quadratic susceptibilities and substantial stability of nonlinear optical (NLO) properties after the poling. Tetraglycidyl ether of quercetin forms the polymer of lower quadratic susceptibility, which demonstrates noticeable relaxation process resulting in decrease of the NLO effect.It is supposed that the difference of the NLO properties is due to peculiarities of physical network of the polymers, namely to the ratio between numbers of hydrogen bonds formed by hydroxyl groups of chromophore fragments and by the ones of interfragmental parts of the polymeric chains.     

具有可调节三阶非线性光学性能的偶氮苯金属配合物

具有刺激响应性的三阶非线性光学材料由于其可控的光物理性质而受到了广泛的关注.本文设计并合成了两种少见的金属配合物三阶非线性光开关,它们在性能转换、多功能性和响应速度等方面远优于同类光开关材料.三阶非线性光学性能测试结果表明,该金属配合物在光照前同时具有反饱和吸收和自散焦折射行为.而在光照后,吸收行为立即消失且自散焦折射...     

Effect of halogen substitution on azo-naphthol dye based poly(alkyloxymethacrylate)s and their Z-scan measurements

A series of photo addressable polymers bearing azo-naphthol moiety in the polymer side chain containing polymethacrylate backbone were synthesized for NLO applications. Various halogen atoms were substituted in the para position of the side chain azobenzene, and the effects of the substituents were investigated. The polymers were characterized by UV, FT-IR, ¹H-NMR and ¹³C-NMR spectroscopy. The photoisomerization property of all the polymers shows a clear dependence on the size of the halogen, indicating the rate of the switching time in the increasing order of F > Cl > Br > I. The glass transition temperature and thermal stability of the polymers were analyzed by DSC and TGA respectively. The third order nonlinear optical properties of the polymer film were measured by the Z-scan technique using Ar-ion laser and exhibited negative optical nonlinearity. The results revealed that these polymers possess potential applications in nonlinear optics and the value of nonlinear susceptibility for the iodine substituted polymer is higher than the other halogen substituted polymers chosen in the study.     

光致变色聚合物的光学性能与应用

综述了光致变色聚合物的光学性能及应用的近期研究进展，首先，介绍了光诱导双折射及双色现象形成机理及实验方法，并讨论了分子结构与外部条件对上述现象的影响。其次，介绍了光致变色聚合开关线性光学性能和应用。如由光助极化和全光极化形成的光开关现象将有可能引起数字存储或光-光开关等新装置的出现，最后，简单说明了光诱导表面光栅在近几年的研究情况，并分析了它们在全息图像存贮，光学过滤器及共振电偶中的潜在应用。     

Photophysical and electrochemical properties of donor-acceptor conjugated oligomers based on 3,4-ethylenedioxythiophene and deficient rings

The photophysical and electrochemical properties of four novel donor-accepter (D-A) conjugated oligomers a-d based on 3,4-ethylenedioxythiophene (EDOT) and electrondeficient heterocycle rings were investigated. The UV-vis absorption spectroscopy, fluorescence emission spectroscopy and cyclic voltammertry studies suggest that the oligomers are expected to provide enhanced charge-transporting properties for the development of efficient electroluminescent materials. Furthermore, the third-order nonlinear optical (NLO) measurements made by Z-scan technique indicate that they have good third-order NLO response and are desired materias for fabricating nonlinear photonic devices. In the solid state of these oligomers, a strong tendency of self-assembled structure was also revealed by X-ray diffraction (XRD) patterns in powder.     

Controlled bistability by using array defect layers in one-dimensional nonlinear photonic crystals

Using analytical modeling and detailed numerical simulations, we investigate the input-output transmission regimes in one-dimensional (1D) nonlinear photonic crystal including array defect layers. A coupled-mode system is derived from the Maxwell equations and analyzed for the stationary-transmission regime in the new proposed structure. Using the idea about introducing defect layers into 1D nonlinear photonic crystals, a new method for creating and controlling optical bistability is proposed. The periodic optical structures with array defect layers can be used as all optical switches between lower- and higher-transmissive states, whereas it possesses one jumping from a low-transmissive state to a transparent state.     

Synthesis, characterization, and nonlinear optical properties of donor–acceptor conjugated polymers and polymer/Ag nanocomposites

Two new donor–acceptor (D–A) conjugated polymers P1 and P2 containing 3,4-didodecyloxythiophene and 1,3,4-oxadiazole units are synthesized via Wittig reaction methodology. Cyclic voltammetry studies reveal that the polymers are both p and n dopable, and possess low-lying LUMO energy levels (?3.34?eV for P1 and ?3.46?eV for P2) and high-lying HOMO energy levels (?5.34?eV for P1 and ?5.27?eV for P2). The optical band gap of the polymers is in the range of 2.25–2.29?eV, calculated from the onset absorption edge. The polymers emit orange to yellow light in the film state when irradiated with a UV light. The synthesized polymers are used to prepare polymer nanocomposites with different wt% of silver nanoparticles. The polymer nanocomposites are characterized by UV–Vis absorption spectroscopy, field emission scanning electron microscopy, and thermogravimetric analysis. Both polymers and polymer/Ag nanocomposites show good thermal stability with onset decomposition temperature around 300?°C under nitrogen atmosphere. The nonlinear optical properties of polymers and polymer/Ag nanocomposites are measured by Z-scan technique. Both polymers and polymer nanocomposites show a good optical limiting behavior. Nearly five times enhancement in the nonlinear optical properties is observed for polymer/Ag nanocomposites. The value of effective two-photon absorption coefficient (β) is in the order of 10^?10–10^?11?m/W. These results indicate that the synthesized polymers (P1 and P2) and their Ag nanocomposites are expected to be good candidates for application in photonic devices.     

Mesoscale dynamics and cooperativity of networking dendronized nonlinear optical molecular glasses

First, molecular scale insight into the mobility of a novel class of organic materials for photonic applications with electro-optical activities larger than 300 pm/V is presented. A representative second order nonlinear optical (NLO) material of this class of self-assembling molecular glasses involving quadrupolar phenyl-perfluorophenyl (Ph-PhF) interactions is analyzed based on its molecular relaxation phenomena and phase behavior. Thereby, a new and straightforward nanoscale methodology, involving shear modulation force microscopy and intrinsic friction analysis is introduced. It provides both the submolecular enthalpic and entropic dynamics in nanoconstrained systems (e.g., ultrathin films), and thus, insight into local motion of single molecules due to dissociation of Ph-PhF pairs as well as the cooperative dynamics of the assembled network. This nanoscale model-independent thermomechanical methodology is shown to be very effective in fundamentally evaluating appropriate poling conditions of organic NLO materials. It promises to be a straightforward analysis tool to guide organic material synthesis from a molecular mobility perspective, particularly for applications that impose nanoscale constraints on the system.     

Synthesis and the third-order non-linear optical properties of new azobenzene-containing side-chain polymers

A new series of aromatic azobenzol compounds containing vinyl have been designed as monomers. The azobenzene-containing side-chain polymers containing azo NLO chromophore in each side chain have been synthesized via free radical polymerization. FT-IR, elemental analysis and ¹H NMR were performed to characterize the azo monomers. The molecular weight of the polymers and their distribution were determined by gel permeation chromatography (GPC). The third-order NLO coefficient of azo monomers and their polymers were measured by degenerated four wave mixing (DFWM) technique. As a result, the enhancement of the molecular conjugation and the increase of the NLO chromophore concentration in the molecular chain contribute much to heightening the third-order NLO effect. The electronic effect of substituent on the azobenzol group and the push–pull electronic structure contributes much to enhancing the NLO property.     

Nonlinear optical properties of the PbS nanorods synthesized via surfactant-assisted hydrolysis

PbS nanorods were synthesized by surfactant-assisted homogenous hydrolysis. The products were characterized by UV–vis spectrophotometer, X-ray powder diffraction (XRD) and transmission electron microscope (TEM). PbS nanorods were measured by the Z-scan technique to investigate the third-order nonlinear optical (NLO) properties. The result of the NLO measurements shows that the PbS nanorods have the third-order nonlinear optical properties of both NLO absorption and NLO refraction with self-focusing effects. The nonlinear absorption coefficient and refractive index of the PbS nanorods are 2.16 × 10^− 9 m/W and 3.52 × 10^− 16 m²/W respectively.     

非线性光学聚合物材料的研究进展

非线性光学聚合物是新型的具有很高实用价值的功能材料，在光电子信息领域具有广阔的应用前景。文中简要介绍了非线性光学理论和极化原理，综述了非线性光学聚合物材料的研究现状及进展，首重阐述了掺杂型、侧主链型、交联型及共轭型等非线性光学聚合物的结构与性能，展望了今后的研究方向。     

Electro-tunable optical diode based on photonic bandgap liquid-crystal heterojunctions

Manipulation of light is in strong demand in information technologies. Among the wide range of linear and nonlinear optical devices that have been used, growing attention has been paid to photonic crystals that possess a periodic modulation of dielectric function. Among many photonic bandgap (PBG) structures, liquid crystals with periodic structures are very attractive as self-assembled photonic crystals, leading to optical devices such as dye lasers. Here we report a new hetero-PBG structure consisting of an anisotropic nematic layer sandwiched between two cholesteric liquid-crystal layers with different helical pitches. We optically visualized the dispersion relation of this structure, displaying the optical diode performance: that is, the non-reciprocal transmission of circular polarized light at the photonic-bandgap regions. Transmittance spectra with circularly polarized light also reveal the diode performance, which is well simulated in calculations that include an electro-tunable diode effect. Lasing action was also confirmed to show the diode effect with a particular directionality.     

Synthesis and the third-order non-linear optical properties of new azobenzene-containing side-chain polymers

A new series of aromatic azobenzol compounds containing vinyl have been designed as monomers. The azobenzene-containing side-chain polymers containing azo NLO chromophore in each side chain have been synthesized via free radical polymerization. FT-IR, elemental analysis and ¹H NMR were performed to characterize the azo monomers. The molecular weight of the polymers and their distribution were determined by gel permeation chromatography (GPC). The third-order NLO coefficient of azo monomers and their polymers were measured by degenerated four wave mixing (DFWM) technique. As a result, the enhancement of the molecular conjugation and the increase of the NLO chromophore concentration in the molecular chain contribute much to heightening the third-order NLO effect. The electronic effect of substituent on the azobenzol group and the push–pull electronic structure contributes much to enhancing the NLO property.     

Mechanochromic Photonic Gels

Polymer gels are remarkable materials with physical structures that can adapt significantly and quite rapidly with changes in the local environment, such as temperature, light intensity, electrochemistry, and mechanical force. An interesting phenomenon observed in certain polymer gel systems is mechanochromism – a change in color due to a mechanical deformation. Mechanochromic photonic gels are periodically structured gels engineered with a photonic stopband that can be tuned by mechanical forces to reflect specific colors. These materials have potential as mechanochromic sensors because both the mechanical and optical properties are highly tailorable via incorporation of diluents, solvents, nanoparticles, or polymers, or the application of stimuli such as temperature, pH, or electric or strain fields. Recent advances in photonic gels that display strain‐dependent optical properties are discussed. In particular, this discussion focuses primarily on polymer‐based photonic gels that are directly or indirectly fabricated via self‐assembly, as these materials are promising soft material platforms for scalable mechanochromic sensors.     

聚酰亚胺基二阶非线性光学材料

二阶非线性光学材料作为光电子中的关键材料已引起了研究人员极大的兴趣。而聚酰亚胺作为一种二阶非线性光学材料的基体除了具备有机聚合物的共有优点如易加工成型外,还比其它聚合物基二阶非线怀光学材料具有更高的玻璃化转变温度,更优异的耐热性能、电性能和机械性能,是目前被选用最多的二阶非线性光学材料的聚合物基体之一。本文对近年来聚酰亚胺基二阶非线性光学材料的制备、性能研究以及极化松驰方面的研究进展进行了评述。     

Picosecond nonlinear optical studies of gold nanoparticles synthesised using coriander leaves (Coriandrum sativum)

The results are presented from the experimental picosecond nonlinear optical (NLO) studies of gold nanoparticles synthesised using coriander leaf (Coriandrum sativum) extract. Nanoparticles with an average size of ～30?nm (distribution of 5–70?nm) were synthesised according to the procedure reported by Narayanan et al. [Mater. Lett. 2008, 62, 4588–4591]. NLO studies were carried out using the Z-scan technique using 2?ps pulses near 800?nm. Open-aperture data suggested saturation absorption as the nonlinear absorption mechanism, whereas closed-aperture data suggested a positive nonlinearity. The magnitude of third-order nonlinearity was estimated to be (3.3?±?0.6)?×?10^?13?esu. A solvent contribution to the nonlinearity was also identified and estimated. A comparison is attempted with some recently reported NLO studies of similar gold nanostructures.     

The growth of l-Glutamic acid hydrochloride crystals by Sankaranarayanan-Ramasamy (SR) method

An efficient semiorganic nonlinear optical crystal l-Glutamic acid hydrochloride has been grown by using the novel uniaxial crystal growth method of Sankaranarayanan and Ramasamy with a slight modification in the experimental setup. This method allows the crystals to grow in one specified axis with well developed facet. The grown crystal has a cylindrical morphology with good optical quality. The grown crystal has been characterized by powder X-ray diffraction and UV-Vis-NIR analyses. The NLO efficiency of the crystal has been confirmed by using the Kurtz powder technique.