Characterization of nonlinear optical absorption and refraction

We discuss the characterization of nonlinear optical processes that give rise to changes in the absorption coefficient and refractive index. We primarily concentrate on methods for determining the dominant nonlinearities present in condensed matter and the responsible physical mechanisms. In extensive studies of a wide variety of material, we have found that there is seldom a single nonlinear process occurring. Often several processes occur simultaneously, sometimes in unison, sometimes competing. It is necessary to experimentally distinguish and separate these processes in order to understand and model the interaction. There are a variety of methods and techniques for determining the nonlinear optical response, each with its own weaknesses and advantages. In general, it is advisable to use as many complementary techniques as possible over a broad spectral range in order to unambiguously determine the active nonlinearities. Here we concentrate on the use of nonlinear transmittance, Z-scan and degenerate four-wave mixing experiments as applied to polycrystalline and single crystal semiconductors and dielectric materials.     

含平面共轭构型的非线性光学晶体

紫外非线性光学晶体是组成紫外固态激光器的关键材料。目前,紫外非线性光学晶体主要依赖硼酸盐晶体,但已有的硼酸盐晶体并不能完全满足应用需求,而进一步研发新型硼酸盐非线性光学晶体难度不断增大,因此开拓新的材料体系显得尤为迫切。从硼酸盐结构与非线性光学效应关系可知,含有平面共轭基团的硼酸盐具有大的倍频系数、合适的双折射率和短的紫外截止边等特性,因此平面共轭基团是硼酸盐非线性光学晶体的核心功能基元。基于几何构型拓展平面共轭基团研究是探索新体系紫外非线性光学晶体材料的重要思路和关键环节。基于此,本团队提出以具有平面三角共轭结构的碳酸盐、硝酸盐、胍盐和具有平面六元环共轭结构的氰尿酸氢盐、巴比妥酸氢盐等化合物为研究对象,拓展紫外非线性光学晶体材料的探索范围。本文将主要介绍本团队近年来在碳酸盐、硝酸盐、胍盐、氰尿酸氢盐、巴比妥酸氢盐紫外晶体探索方面取得的研究成果。     

Recent advances with electro-optic polymers

Abstract

In recent years the electro-optic polymers emerged as an important branch of material science. This growth and interest is fundamentally motivated by practical application of these materials in second-order nonlinear optics and in waveguiding configuration. Indeed, these materials marry excellent optical quality of amorphous σ bonded polymers with enhanced first hyperpolarizability of imbedded organic nonlinear optical molecules. Although a big progress was achieved with them, concerning particularly the science, understanding and applications, some problems remain still incompletely solved, particularly the stability of induced polar order by the application of external electric field and the molecule aggregation. In this review paper we recall techniques of thin film fabrication, poling, characterization of NLO properties and discuss more precisely problems of molecule aggregation as well as the temporal decay of polar order. A novel 3D second-order NLO chromophores, namely the [2] paracyclophanes, which may help to limit the aggregation, are proposed. We show, in particular, that this molecule can be poled in doped PMMA thin films. Practical applications of electro-optic polymers are also reviewed and discussed.     

Controllable space selective precipitation of copper nanoparticles in borosilicate glasses using ultrafast laser irradiation

Transparent glasses containing copper nanoparticles are promising materials for ultrafast all-optical switches in the THz region due to their wide range of resonant absorption frequencies, ultrafast time response, as well as large third-order nonlinear optical coefficients associated with the surface plasmon resonance (SPR) in the visible region. In this paper, three dimension controllable precipitation of copper nanoparticles inside a borosilicate glass by irradiation of femtosecond laser pulses is studied. According to the designed program, different patterns made up of copper nanoparticles can be induced inside the glass sample. Absorption spectra are used to confirm the precipitation of copper nanoparticles. The precipitated nanoparticles can be space-selectively “dissolved” by the second time femtosecond laser irradiation. The involved mechanisms are discussed.     

Solidification behaviour of organic nonlinear optical crystals

A representative rather than exhaustive review has been given on the solidification behaviour of organic nonlinear optical crystals. Many of the developments reported here represent quick experimental responses to the rapid theoretical advances made in the field of nonlinear optics. The article is divided into four parts. The first part deals with the characteristics of the organic nonlinear materials and need for large single crystals. The second and third parts are devoted to the thermophysical properties and experimental studies on crystallization processes. Here, recent work by authors is reviewed on the purification of source material, solidification behaviour and crystal growth. Various interactions between morphology, microsegregation, defects, growth velocity and temperature gradient are discussed. Specific examples of substituted anilines are presented. In the fourth section a stronger interaction is suggested between optical physicists and crystal growers to understand the problems of inhomogeneity, stress, damage threshold and doping in the organic crystals.     

ZnGeAs2多晶合成与表征

ZnGeAs2是黄铜矿结构的三元化合物半导体材料,在红外非线性光学方面有重要应用前景.本文探讨了ZnGeAs2多晶的形成途径和合成机理,报道了一种ZnGeAs2多晶合成方法.以高纯(6N)Zn、Ge、As单质为原料,按化学计量比,富Zn1‰和As2‰配料,采用双温区合成方法,辅以机械、温度振荡和梯度降温的合成工艺,合成出均匀致密的单相ZnGeAs2多晶.经XRD和EDS分析表明:合成产物为黄铜矿结构的单相ZnGeAs2多晶,晶胞常数为a=b=0.56745 nm,c=1.11580 nm,与标准PDF卡片(No.730397)一致;各组成元素的原子比Zn∶Ge∶AS=1.00∶0.98∶1.95,接近理想化学计量比.上述分析结果表明,合成产物可用于ZnGeAs2单晶生长,为进一步研究ZnGeAs2晶体的非线性光学性能和应用奠定了较好的基础.     

LiInS2多晶原料的合成与性能

本文研究了高纯LiInS2多晶原料的合成及性能.LiInS2晶体是一种极具吸引力的晶体,可以应用于红外区域的非线性光学频率变换.一般来说,含锂硫族化合物制备非常困难,因为锂极易被氧化,且腐蚀石英管.而且,硫族元素高的蒸气压会导致石英安瓿爆炸.本文采用两种方法合成了LiInS2多晶原料,对所获LiInS2多晶原料进行了X射线粉末衍射和差示扫描量热分析.     

Structural dependence of ultrafast third-order optical nonlinearity of Ge–Ga–Ag–S chalcogenide glasses

Ultrafast third-order optical nonlinearity of Ge–Ga–Ag–S chalcogenide glasses at the wavelength of 820 nm has been measured using femtosecond time-resolved optical Kerr (OKE) technique. The results show that Ge–Ga–Ag–S glasses have large third-order optical nonlinear susceptibility, χ⁽³⁾ and the response time is also subpicosecond, which are predominantly due to the ultrafast distortion of electron cloud surrounding the balanced positions of Ge, Ga, Ag and S atoms. What’s more, a strong dependence of χ⁽³⁾ on the composition and microstructure of these glasses was found which shows that [GeS₄] and [GaS₄] tetrahedra play an important role on the third-order optical nonlinearity. These Ge–Ga–Ag–S chalcogenide glasses would be expected as promising materials applied on all-optical switching devices.     

LiInS_2多晶原料的合成与性能(英文)

本文研究了高纯LiInS2多晶原料的合成及性能。LiInS2晶体是一种极具吸引力的晶体,可以应用于红外区域的非线性光学频率变换。一般来说,含锂硫族化合物制备非常困难,因为锂极易被氧化,且腐蚀石英管。而且,硫族元素高的蒸气压会导致石英安瓿爆炸。本文采用两种方法合成了LiInS2多晶原料,对所获LiInS2多晶原料进行了X射线粉末衍射和差示扫描量热分析。     

Optical Materials Based on Nanoscaled Guest/Host Composites

Abstract

Ordered periodic microporous and mesoporous materials allow the construction of composites with many guest types, e. g. organic molecules, inorganic ions, semiconductor clusters or polymers. These guest/host materials combine high stability of the inorganic host system, new structure forming mechanisms due to the confinement of guests in well defined pores, and a modular composition. This could lead to new optical materials which are described in this paper by examples in switches, nonlinear optics and lasers.     

Amino acids-precursors for synthesizing nonlinear optical materials

Some new nonlinear optical materials were synthesized from amino acids l-arginine and l-valine and single crystals were grown from their aqueous solution by solvent evaporation method at constant temperature and slow cooling method. The synthesized materials were identified by carbon, hydrogen, nitrogen (CHN) test and single crystal X-ray diffraction (XRD) analysis. The grown crystals were characterized by measuring their thermal, optical and mechanical properties by Differential Thermal Analysis (DTA), Thermo Gravimetric Analysis (TGA), powder second harmonic generation (SHG) efficiency, damage threshold and microhardness measurements. Our study shows that halides of l-arginine and l-valine are promising Nonlinear Optical (NLO) materials having Second Harmonic Generation (SHG) efficiency, mechanical and thermal stability greater than other semi-organic NLO materials. But among the halide salts, l-valine hydrobromide (LVHBr) emerged as most promising NLO materials as far as SHG efficiency, and damage threshold are concerned.     

Optical Field Induced Scattering in Polymer Dispersed Liquid Crystal Films

Abstract

Polymer dispersed liquid crystals are composite materials consisting of inclusions of liquid crystalline materials dispersed in a polymer binder. If the refractive indices of the constituent liquid crystal and polymer are appropriately matched, then films of these materials may be switched between an optically scattering state and a non–scattering transparent state^1?2 by the application of electric fields which reorient the liquid crystal in the inclusions. In this paper we discuss the response of these materials to intense laser radiation, and examine the mechanisms associated with optical field induced reorientation.     

Linear and non-linear optical properties of 2,5-disubstituted pyrroles supported by a catalyst-free SiO2 sonogel network

The preparation and optical characterization of pyrrole based sol-gel hybrid materials generated by ultrasonic irradiation (Sonogel composites) are presented in this work. Pyrrole compounds were recently synthesized in our group by a modification of the Schulte-Reisch reaction; these molecular systems were dissolved at different concentrations in tetrahydrofuran (THF) and optimally embedded into a catalyst-free SiO₂ sonogel network. For this purpose, we exploited the novel catalyst-free (CF) sonolysis route to produce highly pure sol-gel glasses, generated via sonochemical reactions. This approach has been recently developed in our research group and has been successfully implemented to develop several hybrid composites for optical applications. By this method, homogeneous and stable solid-state hybrid samples suitable for optical characterization can be produced. The high porosity exhibited by the sonogel matrix allowed us to prepare several pyrrole doped composites with variable dopant concentration. The linear and nonlinear optical (NLO) properties of these amorphous hybrid structures were determined by absorption- and photoluminescent (PL)-spectroscopies, and by the optical third harmonic generation (THG) techniques, respectively. The implemented catalyst-free sonolysis route produced SiO₂-host networks of high chemical and optical purity, suitable for optical and photonic applications.     

利用化学键方法寻找新型光学晶体

利用化学键的观点定量地研究了一些具有各种晶体结构实用材料的介电性质。采用已建立的化学键方法，分析了这些晶体的介电性质与其组成化学键之间的关系。更进一步，基于晶体的化学键方法提出了一个组合方法用于定量确定具有相似晶体结构材料的介电性质。从目前的工作中可以推导出光学晶体非线性起源的结构信息，因此可以在一定程度上帮助人们开展非线性光学晶体工程的研究工作。     

Femtosecond optical Kerr effect study of amorphous chalcogenide films

The non-resonant third-order non-linear optical properties of some amorphous chalcogenide films were studied experimentally by the method of the femtosecond optical heterodyne detection of the optical Kerr effect. The real and imaginary parts of the complex third-order optical non-linearity could be effectively separated and their values and signs could be also determined. Amorphous chalcogenide films showed a very fast response in the range of 200 fs under ultrafast excitation. The ultrafast response and large third-order non-linearity are attributed to the ultrafast distortion of the electron orbitals surrounding the average positions of the nucleus of chalcogen atoms. The high third-order susceptibility and a fast response time of amorphous chalcogenide films make them promising materials for application in advanced techniques especially in optical switching.     

Organic inclusion complex strategy for designing nonlinear optical crystals for ultraviolet applications

Based on Molecular Engineering and Crystal Engineering concepts, a new method for designing nonlinear optical (NLO) crystal materials, the Organic Inclusion Complex (OIC) method has been demonstrated. In defining an appropriate optical transparent range with respect to the Molecular Engineering method, small organic molecules containing n-π conjugation were selected as “second order harmonic generation (SHG)-active units”(guests). Together with the Crystal Engineering method, chiral molecules were used as “molecular scaffolding” (hosts) to combine with the “SHG-active units” by hydrogen bonds. The former can provide a nonlinear optical effect. The latter leads to the OIC with a noncentrosymmetric structure and are expected to enhance the macroscopic nonlinearity in a synergistic mode of guest and host by inducing the guest molecular dipole alignment as well as other properties, such as thermal stability, mechanical strength and ease of growth. Here, we report two new inclusion complex crystals, urea-(d)tartaric acid (UDT) and urea-(dl)tartaric acid (UDLT) (here, d means dextral and dl means racemic). UDT and UDLT crystals belong to P2,2,2, and P2, space group, respectively. Bulk size crystals with high optical quality were successfully obtained from aqueous solution by using a temperature-lowering method. The experimental results show that these two crystals demonstrate higher NLO effects and shorter wavelength cutoff.     

Effect of different metal ions on structural,thermal, spectroscopic and optical properties of ATCC and ATMC single crystals

A novel metal‐organic coordination complex nonlinear optical crystals, tri‐allylthiourea cadmium chloride [(CdCl₂(AT)₃] and tri‐allylthiourea mercury chloride [(HgCl₂(AT)₃] abbreviated as ATCC, ATMC (AT is Allylthiourea i.e.,CH₂=CHCH₂NHCSNH₂) has been synthesized and grown as single crystals. It was synthesized in deionised water and further recrystallized to improve its purity. Single crystals of the allylthiourea co‐ordination complex nonlinear optical crystals tri allylthiourea cadmium chloride (ATCC) with dimensions of 14x14x10 mm³ and tri allylthiourea mercury chloride (ATMC) with dimensions of 15x15x12 mm³ were grown successfully from aqueous solution by solvent evaporation as well as by temperature lowering method. It exhibits powder SHG efficiencies higher than that of a well known organic NLO crystal Urea. The solubility of the as grown crystals was estimated from the aqueous solution and the effect of different metal ions on the grown crystals, structural, thermal, spectral and optical properties were analyzed. XRD studies the reveals the same structure of both materials. Influence of the different central metal (Cd and Hg) atoms, changing the thermal properties of the materials when NLO complexes formed with the common ligand allylthiourea. The metal co‐ordination was confirmed form the spectroscopic analysis. From the UV transmittance studies, red shift was from the transparency cut‐off wavelengths. The value is 285nm for ATCC is and is 335nm ATMC, Non‐linear an optical study confirms the suitabilities of the as grown crystals for the non linear optical applications. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and Characterization of Nonlinear Optical Crystal Materials: Cadmium Mercury Thiocyanate and its Lewis Base Adducts

Cadmium mercury thiocyanate (CdHg(SCN)₄, CMTC) and its two lewis base adducts: cadmium mercury thiocyanate dimethyl‐sulphoxide (CdHg(SCN)₄(H₆C₂OS)₂, CMTD) and cadmium mercury thiocyanate glycol monomethyl ether (CdHg(SCN)₄(C₃H₈O₂), CMTG) have been discovered as nonlinear optical (NLO) crystal materials. Their structural, optical and physicochemical properties were characterized by X‐ray powder diffraction (XRPD), infrared spectroscopy, vis/UV/NIR spectra and thermal analysis. It is discovered that their transparency cutoffs lie in the UV region and CMTD crystals possess the shortest cutoff wavelength among the three crystal materials.     

Photoprogrammable molecular hybrid materials for write-as-needed optical devices

The application of photosensitive materials to provide immediately configurable optical device functionality in integrated photonic systems has motivated an examination of the unique materials requirements associated with this alternative operational mode. In this case, a reliable photoinduced index change is needed when photopatterning under non-laboratory conditions utilizing compact, integrable optical sources. Molecular hybrid thin films, based on inorganic, Group IVA linear-chain polymers, are investigated in terms of excitation (writing) wavelength tuning through molecular modification and the influence of environmental conditions and thermal history on the photosensitive response observed. In general, a significant photoinduced refractive index change (with magnitude greater than 10⁻² at 632.8 nm) is found to be retained as the lowest energy absorption band (associated with the Group IVA conjugated backbone structure) is shifted with changes in side-group identity and backbone composition. In addition, the photosensitive response of a representative polysilane composition (poly[(methyl)(phenyl)silylene]) is observed to be strongly dependent on the local atmospheric composition during photoexposure, a key issue in the effective in-situ patterning of optical structures.     

A new-type composite film of cholesteric liquid crystal doped with PCBM for laser-damage prevention in both visible and near-infrared region

Nowadays, with the increasing use of high-power laser, research and development of laser-damage prevention materials with multifunctional features and wideband wavelengths are urgent and indispensable. In the paper, cholestric liquid crystal (ChLC) is first proposed to be doped with a high-efficiency optical limiting material, 6, 6-phenyl C61-butyric acid methyl ester (PCBM), to fabricate a new-type laser-damage-prevention film. The ChLCs have the desired reflection wavelengths covering 750–2300 nm, which is an effective and potential candidate for the prevention of continuous or tuneable laser in near infrared (NIR) region. Meanwhile, the solubility of PCBM in LC and its nonlinear absorption property of are discussed, and it was proved that the good solubility of PCBM in LC contributed to the excellent nonlinear absorption of mixture (LC doped with PCBM). Taking advantages of this phenomenon, a novel composite film of ChLCs doped with PCBM is prepared by UV polymerization. As a result, the composite film not only performs broadband reflection in NIR region, but also exhibits a strong nonlinear absorption and excellent optical limiter properties in visible region, which proves the film's potential application in laser damage prevention.