有机和金属有机非线性光学晶体材料

非线性光学材料是激光技术的重要物质基础之一,是高技术研究的一个组成部分。二十多年来,非线性光学材料的研究经历了无机晶体、有机材料的阶段,现在又开始了金属有机非线性光学材料的探索。本文拟综述有机和金属有机二阶非线性光学晶体材料的研究进展,而不讨论高分子材料以及三阶非线性光学效应。鉴于刊物读者的特     

有机非线性光学

由于有机化合物具有非线性光学系数高、响应快等特点,近年来有机非线性光学研究受到了很大的重视。本文从有机非线性光学材料的结构特点出发,综述了典型的四类有机二阶非线性光学晶体方面的研究进展,对三阶材料也作了简要的介绍。     

二阶非线性光学聚合物材料

非线性光学材料是一类具有很高实用价值的功能材料。综述了聚合物二阶非线性光学材料的研究、极化聚合物在实用化研究方面取得的新进展,介绍了提高极化聚合物生色团高温取向稳定性、设计合成光损失较小的生色团以及优化聚合物主体的新方法。     

溶剂化变色方法测定分子二阶极化率

有机非线性光学材料的研究现正在许多化学实验室中开展了起来。与此相适应,人们寻求一种相对简便易行的分子二阶极化率的测定方法,溶剂化变色就是这样一种方法。本文即介绍用这一方法测定分子二阶极化率的情     

二阶非线性光学聚合物材料的最新研究进展

随着激光技术与光纤通信技术的蓬勃发展 ,迫切要求提高非线性光学极化聚合物的性能 ,以满足器件化的要求 ,这就需要从分子设计和极化方法等方面进行研究和优化。本文以聚合物主链结构为线索 ,以非线性光学性能为依据 ,介绍了二阶非线性光学聚合物的最新研究进展 ,并展望了该类聚合物在光通信领域的应用前景     

静电纺丝制备有机盐类非线性光学材料纳米纤维

采用静电纺丝技术制备的有机非线性光学材料纳米纤维可有效控制非线性光学材料的分子取向,其生色团可实现与有机单晶类似的优化排列结构,表现出了与纯生色团分子相近的宏观二阶非线性光学性质。 本文将有机盐类非线性光学材料掺杂在聚乙烯吡咯烷酮中制备出了具有各向异性结构且表面光滑、排列有序的纳米纤维薄膜,Kurtz非线性测试结果表明,随着薄膜厚度增加,其二次谐波信号强度成正比增大。     

有机二阶非线性光学聚合物的研究进展

非线性光学材料在激光、光通信、光处理、高频电光器件及太赫兹等方面具有重要的应用。相比传统无机非线性光学材料,有机二阶非线性光学材料具有电光系数高、响应速率快、易加工等优点。近年来,基于有机非线性光学材料的研究成为热门领域,高频电光器件、太赫兹器件等都受到了业内广泛关注。本文综述了不同种类的有机二阶非线性光学材料的研究进展和未来的发展方向。此类材料的电光性能和取向稳定性可以通过分子设计策略和化学合成、发色团与聚合物的结构关系及掺杂技术等进行有效的调控,但是研发满足实际应用且综合性能优异的有机非线性光学材料仍面临诸多挑战。     

尿素分子团簇线性和一阶非线性光学极化率的理论计算

检验分子晶体非线性光学极化率的可加性,对于确认有向气体模型(Oriented-Gas Model) 具有重要的科学意义,对探索新型实用的分子非线性光学材料也有实际的意义。本文对尿素晶体中分子簇非线性光学极化率的可加性做了详尽的理论研究。首次做到了尿素分子最近邻排布团簇的非线性光学极化率的从头算,从而扩展了前人的工作。研究结果有效地确认了有向气体模型。同时,我们还提出了壳层结构模型 (Shell-Structure Model),用以解决有向气体模型中的缺陷,可实现更为有效可靠地计算晶体宏观非线性光学系数。     

盐酸氨基脲的二阶非线性光学性质研究

非线性光学(NLO)材料在光学信息处理、远程通讯等光电子学领域有着重要的应用,有效地预测和设计出二阶非线性光学材料所必需的非中心对称晶体,提高材料的综合性能是这一领域的研究热点。标题化合物盐酸氨基脲是以尿素为分子母体的有机离子型化合物,具有将有机和无机材料的优异性能集于一身的结构优势,是综合性能优的材料之一。     

从美国化学文摘的统计看分子非线性光学的发展

由美国化学文摘１９９１～１９９５年期间收录的有关非线性的论文的统计表明，分子非线性光学材料（尤其是二阶极化聚合物）的论文所占比重比其他方面的论文以更快的速度增长，本文还由１９９５年度的统计结果分析了极化聚合物研究的现状和发展趋势。     

Covalent Organic Frameworks as Emerging Nonlinear Optical Materials

The vastness of organic synthetic strategies and knowledge of reticular chemistry have made covalent organic frameworks (COFs) one of the most chemically and structurally diverse class of materials with potential applications ranging from gas storage, molecular separation, and catalysis to energy storage and magnetism. Recently, this class of porous materials has garnered increasing interest as potential nonlinear optical (NLO) materials. Traditionally, inorganic crystals, small-molecule organic chromophores, and oligomers have been studied for their NLO response. Nevertheless, COFs offer significant advantages over existing NLO materials in terms of higher mechanical strength, thermochemical stability, and extended conjugation. Herein, we discuss crucial aspects, terminology, and measurement techniques related to NLO, followed by a critical analysis of the design principles for COFs with NLO response. Furthermore, we touch on selected potential applications of these NLO materials. Finally, future prospects and challenges of COFs as NLO materials are discussed.     

Organic Polymeric and Non-Polymeric Materials with Large Optical Nonlinearities

Nonlinear optical properties are a sensitive probe of the electronic and solid-state structure of organic compounds and as a consequence find various applications in many areas of optoelectronics including optical communications, laser scanning and control functions, and integrated optics technology. Because of their strongly delocalized π electronic systems, polymeric and non-polymeric aromatic compounds show highly nonlinear optical effects. Nowadays, polymer chemists are able to tailor specific materials properties for various applications. Some organic substances with π electronic systems exhibit the largest known nonlinear coefficients, often considerably larger than those of the more conventional inorganic dielectrics and semiconductors, and thus show promise for thin-film fabrication, allowing the enormous function and cost advantages of integrated electronic circuitry. The electronic origins of nonlinear optical effects in organic π electronic systems are reviewed, with special emphasis being given to second-order nonlinear optical effects. Methods for measuring nonlinear optical responses are outlined, and the critical relationships of the propagation characteristics of light to observed nonlinear optical effects and to solid-state structure are discussed. Finally, the synthesis and characterization of organic crystals and polymer films with large second-order optical nonlinearities are summarized.     

Study of Linear and Nonlinear Optical Properties of Four Derivatives of Substituted Aryl Hydrazones of 1,8‐Naphthalimide

Four 1,8‐naphthalimide hydrazone molecules with different electron‐donating groups have been applied in the study of linear and nonlinear optical (NLO) properties. These compounds showed strong green emission in solution. Their NLO properties such as two‐photon absorption (TPA) behavior with femtosecond laser pulses ca. 800 nm and excited‐state absorption (ESA) behavior with nanosecond laser pulses at 532 nm were investigated. Compound 4 presented the largest two‐photon cross section (550 GM) among them due to two factors: the conjugated length of compound 4 is the longest and the electron‐donating ability of compound 4 is the strongest. Different from TPA behavior, compound 2 showed the best nonlinear absorption properties at 532 nm and its nonlinear absorption coefficient and third‐order nonlinear optical susceptibilities χ ⁽³⁾ were up to 1.41×10^?10 MKS and 4.65×10^?12 esu, respectively. Through the modification of the structure, the nonlinear optical properties of these compounds at different wavelengths (532 and 800 nm) were well tuned. The great broad‐band nonlinear optical properties indicate hydrazones are good candidates for organic nonlinear optical absorption materials.     

Hybrid Double Perovskite Derived Halides Based on Bi and Alkali Metals (K,Rb): Diverse Structures,Tunable Optical Properties and Second Harmonic Generation Responses

Double perovskites (DP) have attracted extensive attention due to their rich structures and wide application prospects in the field of optoelectronics. Here, we report 15 new Bi-based double perovskite derived halides with the general formula of A₂BBiX₆ (A=organic cationic ligand, B=K or Rb, X=Br or I). These materials are synthesized using organic ligands to coordinate with metal ions with a sp³ oxygen, and diverse structure types have been obtained with distinct dimensionalities and connectivity modes. The optical band gaps of these phases can be tuned by changing the halide, the organic ligand and the alkali metal, varying from 2.0 to 2.9 eV. The bromide phases exhibit increasing photoluminescence (PL) intensity with decreasing temperature, while the PL intensity of iodide phases changes nonmonotonically with temperature. Because the majority of these phases are non-centrosymmetric, second harmonic generation (SHG) responses are also measured for selected non-centrosymmetric materials, showing different particle-size-dependent trends. Our findings give rise to a series of new structural types to the DP family, and provide a powerful synthetic handle for symmetry breaking.     

Low loss second‐order non‐linear optical crosslinked polymers based on a phosphorus‐containing maleimide

A series of crossslinked organic and organic/inorganic polymers based on maleimide chemistry have been investigated for second‐order non‐linear optical (NLO) materials with excellent thermal stability and low optical loss. Two reactive chromophores (maleimide‐containing azobenzene dye and alkoxysilane‐containing azobenzene dye) were incorporated into a phosphorus‐containing maleimide polymer, respectively. The selection of the phosphorus‐containing maleimide polymer as the polymeric matrices provides enhanced solubility and thermal stability, and excellent optical quality. Moreover, a full interpenetrating network (IPN) was formed through simultaneous addition reaction of the phosphorus‐containing maleimide, and sol‐gel process of alkoxysilane dye (ASD). Atomic force microscopy (AFM) results indicate that the inorganic networks are distributed uniformly throughout the polymer matrices on a nano‐scale. The silica particle sizes are well under 100 nm. Using in situ contact poling, the r₃₃ coefficients of 2.2–17.0 pm/V have been obtained for the optically clear phosphorus‐containing NLO materials. Excellent temporal stability (100°C) and low optical loss (0.99–1.71 dB/cm; 830 nm) were also obtained for these phosphorus‐containing materials. Copyright © 2004 John Wiley & Sons, Ltd.     

Chiral Side Groups Trigger Second Harmonic Generation Activity in 3D Octupolar Bipyrimidine‐Based Organic Liquid Crystals

The design of efficient noncentrosymmetric materials remains the ultimate goal in the field of organic second‐order nonlinear optics. Unlike inorganic crystals currently used in second‐order nonlinear optical applications, organic materials are an attractive alternative owing to their fast electro‐optical response and processability, but their alignment into noncentrosymmetric film remains challenging. Here, symmetry breaking by judicious functionalization of 3D organic octupoles allows the emergence of multifunctional liquid crystalline chromophores which can easily be processed into large, flexible, thin, and self‐oriented films with second harmonic generation responses competitive to the prototypical inorganic KH₂PO₄ crystals. The liquid‐crystalline nature of these chiral organic films also permits the modulation of the nonlinear optical properties owing to the sensitivity of the supramolecular organization to temperature, leading to the development of tunable macroscopic materials.     

High glass transition temperature chromophore functionalised poly(phenylquinoxalines) for nonlinear optics

New chromophore functionalised second-order nonlinear optical (NLO) poly(phenylquinoxalines) were prepared by reaction of a bis(1,2-dicarbonyl)chromophore monomer and a tetraamine at room temperature. The heterocyclic polymers have high glass transition temperatures (>195 °C) and can therefore be excellent polymeric materials with high poling stabilities of the NLO effect.     

Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long-neglected Nitrides and Popular Chalcogenides

Traditional infrared (IR) nonlinear optical (NLO) materials such as AgGaS₂ are crucial to key devices for solid-state lasers, however, low laser damage thresholds intrinsically hinder their practical application. Here, a robust strategy is proposed for unbiased high-throughput screening of more than 140 000 materials to explore novel IR NLO materials with high thermal conductivity and wide band gap which are crucial to intrinsic laser damage threshold. Via our strategy, 106 compounds with desired band gaps, NLO coefficients and thermal conductivity are screened out, including 8 nitrides, 68 chalcogenides, in which Sr₂SnS₄ is synthesized to verify the reliability of our process. Remarkably, thermal conductivity of nitrides is much higher than that of chalcogenides, e.g., 5×AgGaS₂ (5.13 W/m K) for ZrZnN₂, indicating that nitrides could be a long-neglected system for IR NLO materials. This strategy provides a powerful tool for searching NLO compounds with high thermal conductivity.     

化学键组装稀土/无机/有机聚合物杂化光功能材料的最新研究进展

本文针对近五年来光功能稀土/无机/有机聚合物杂化材料的最新进展进行了评述,其重点着眼于高分子化合物作为构筑基元的发光稀土杂化材料体系的化学键组装.内容主要涉及稀土有机高分子杂化材料、配位键构筑的稀土/无机/有机高分子杂化材料、共价键构筑的稀土/无机/有机高分子杂化材料、自由基聚合构筑的稀土/无机/有机高分子杂化材料几个重要方面.主要结合我们自己的近期研究工作,通过系统总结来展现该领域的研究现状并提出未来展望.