A Full‐Scale Analysis of Absorption Edges in Dye‐Doped Nonlinear Optical Polymers

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTA Novel and Perfectly Aligned Highly Electro−Optic Organic Cocrystal of a Merocyanine Dye and 2,4-DihydroxybenzaldehydeFeng Pan, Man Shing Wong, Volker Gramlich, Christian Bosshard, and Peter GünterView Author Information Nonlinear Optics Laboratory Institute of Quantum Electronics ETH-Hönggerberg, CH-8093 Zürich, Switzerland Cite this: J. Am. Chem. Soc. 1996, 118, 26, 6315–6316Publication Date (Web):July 3, 1996Publication History Received2 April 1996Published online3 July 1996Published inissue 1 January 1996https://pubs.acs.org/doi/10.1021/ja961087khttps://doi.org/10.1021/ja961087krapid-communicationACS PublicationsCopyright © 1996 American Chemical SocietyRequest reuse permissionsArticle Views831Altmetric-Citations92LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information SUBJECTS:Crystal structure,Crystals,Noncovalent interactions,Optical properties,Polarizability Get e-Alerts

The status of advanced nonlinear optical materials is reviewed with regard to the requirements implied by their respective applications. Although many functions utilizing nonlinear optical (NLO) materials have been demonstrated in research laboratories, only a few components have found a place in real systems. While this is partly due to a lack of product development effort, the performance of the materials is not adequate in other cases. III–V based semiconductors show promise for a broad penetration of the field of signal processing for telecommunications and data processing. Linear and nonlinear optical polymers may be applied in assembly and interconnection and in small to medium sized switching matrices. As a prerequisite the anticipated performance has to be achieved, and stability to be demonstrated. Manufacturing maturity is approached by inorganic ferroelectrics, LINbO3 being the most prominent example.

This work is part of a continuing project that is investigating the use of integrated optical (IO) waveguides and optical fibers coated with nonlinear optical (NLO) polymers as electric field sensing devices. The IO waveguides were fabricated using three different techniques: (1) in the NLO polymer itself (on glass and silicon substrates), (2) in glass microscope slides using thin film silver diffusion and silver ion exchange methods, and (3) in thin film optical epoxies. The Ag+ glass and UV cured optical epoxy waveguides were subsequently coated with NLO polymers; the 3-D patterned waveguides provided lateral confinement of the optical wave that propagated in the polymer. A low index buffer layer of polysiloxane glass resin (Owens Illinois GR650E) was needed on the silicon substrates to decrease the propagation loss. The NLO polymers were dip coated or spun on these substrates and were poled with a corona poling technique with fields of the order of 3 MV/cm. Interferometric and polarization rotation methods were used to measure the effects of applied electric fields on the NLO devices at wavelengths of 633, 780, and 830 nm. Electrooptic coefficients were determined and compared with similar coefficients obtained using second harmonic generation methods on the same NLO polymers.

Second-order nonlinear optical (NLO) materials have drawn enormous academic and technological attention attributable to their indispensable role in laser frequency conversion and other greatly facilitated applications. The exploration of new NLO materials with high performances thus has long been an intriguing research field for chemists and material scientists. However, an ideal NLO material should simultaneously satisfy quite a few fundamental yet rigorous criteria including a noncentrosymmetric structure, large NLO coefficients, desired transparent range, large birefringence, high laser damage threshold, and availability of a large-size single crystal. Therefore, the identification of promising compound systems, targeted design, and experience-based syntheses are crucial to discover novel NLO materials working in the spectral region of interest. As an important family of mixed-anion compounds, versatile metal oxyhalides containing metal-centered oxyhalide functional units ([MOmXn] (X = F, Cl, Br, and I)) are becoming a marvelous branch for interesting NLO materials. Especially, when the central metals are d0/d10 transition metals or heavy post-transition metals, a number of novel NLO materials with superior functionalities are expected. Our thorough review on the recent achievements of metal oxyhalides for NLO materials are divided into the fast-growing NLO metal oxyhalides with single type halogen anions and the newly identified NLO metal oxyhalides with mixed halogen anions. Here we mainly focus on the design strategy, structural chemistry, NLO-related properties, and structure–property correlation of the metal oxyhalides with relatively large NLO responses. We hope this review can provide an insight on the rational design and future development of emerging metal oxyhalides for NLO and other applications.

Linear and Nonlinear Polarizability: a Primer Second-Order Nonlinear Optical Processes in Molecules and Solids Third-Order Nonlinear Optical Effects in Molecular and Polymeric Materials Nonlinear Optical Properties of Molecules and Materials Electronic Hyperpolarizability and Chemical Structure Electrooptic Polymer Waveguide Devices: Status and Applications Waveguiding and Waveguide Applications of Nonlinear Organic Materials Nonlinear Optical Materials: The Great and Near Great Donor- and Acceptor-Substituted Organic and Organometallic Compounds: Second-Order Nonlinear Optical Properties Use of a Sulfonyl Group in Materials for Nonlinear Optical Materials: A Bifunctional Electron Acceptor Organic and Organometallic Compounds: Second-Order Molecular and Macroscopic Optical Nonlinearities Chemistry of Anomalous-Dispersion Phase-Matched Second Harmonic Generation Applications of Organic Second-Order Nonlinear Optical Materials Chromophore-Polymer Assemblies for Nonlinear Optical Materials: Routes to New Thin-Film Frequency-Doubling Materials Novel Covalently Functionalized Amorphous *y^2 Nonlinear Optical Polymer: Synthesis and Characterization Second-Order Nonlinear Optical Polyphosphazanes Molecular Design for Enhanced Electric Field Orientation of Second-Order Nonlinear Optical Chromophores Nonlinear Optical Chromophores in Photocrosslinked Matrices: Synthesis, Poling, and Second-Harmonic Generation Thermal Effects on Dopant Orientation in Poled, Doped Polymers: Use of Second Harmonic Generation Organic Polymers as Guided Wave Materials Observing High Second Harmonic Generation and Control of Molecular Alignment in One Dimension: Cyclobutenediones as a Promising New Acceptor for Nonlinear Optical Materials Strategy and Tactics in the Search for New Harmonic-Generating Crystals Development of New Nonlinear Optical Crystals in the Borate Series What is Materials Chemistry? Defect Properties and the Photorefractive Effect in Barium Titanate Defect Chemistry of Nonlinear Optical Oxide Crystals From Molecular to Supramolecular Nonlinear Optical Properties Control of Symmetry and Asymmetry in Hydrogen-Bonded Nitroaniline Materials Molecular Orbital Modeling of Monomeric Aggregates in Materials with Potentially Nonlinear Optical Properties Strategies for Design of Solids with Polar Arrangement Ferroelectric Liquid Crystals Designed For Electronic Nonlinear Optical Applications Model Polymers with Distyrylbenzene Segments for Third-Order Nonlinear Optical Properties Composites: Novel Materials for Second Harmonic Generation Clathrasils: New Materials for Nonlinear Optical Applications Inorganic Sol-Gel Glasses as Matrices for Nonlinear Optical Materials Intrazeolite Semiconductor Quantum Dots and Quantum Supralattices: New Materials for Nonlinear Optical Applications Small Semiconductor Particles: Preparation and Characterization Synthetic Approaches to Polymeric Nonlinear Optical Materials Based on Ferrocene Systems Transition Metal Acetylides for Nonlinear Optical Properties Third-Order Near-Resonance Nonlinearities in Dithiolenes and Rare Earth Metallocenes Nonlinear Optical Properties of Substituted Phthalocyanines Nonlinear Optical Properties of Substituted Polysilanes and Polygermanes Design of New Nonlinear Optic-Active Polymers: Use of Delocalized Polaronic or Bipolaronic Charge States New Polymeric Materials with Cubic Optical Nonlinearities: From Ring-Opening Metathesis Polymerization Polymers and an Unusual Molecular Crystal with Nonlinear Optical Properties Quadratic Electrooptic Effect in Small Molecules Third-Order Nonlinear Optical Properties of Organic Materials

Reversibility between two concomitant polymorphs and their switching ability is demonstrated for the novel organic nonlinear optical (NLO) material Z-3-(3-methoxyphynyl)-2-(4-nitrophenyl)acrylonitrile. The appearances of their concomitant as well as exclusive polymorphic forms were discovered upon systematic crystallization experiments using various solvents. Determination of X-ray crystal structures confirmed that the polymorphs crystallize in centrosymmetric (P21/n) and non-centrosymmetric (Fdd2) space groups. A search using the Cambridge Structural Database revealed that there exist only 10 such polymorphic pairs. Reversible phase transitions and the switching ability between the polymorphs can be achieved via both heat and solvents as stimuli. Structural analysis confirmed that the polymorphs have two-dimensional similarity. Further, quantitative and qualitative analysis of interaction energies based on the UNI force field and energy frameworks indicate that they possess very similar energies, althoug...

Herein the synthesis and the crystal growth of benzoyl valine (BV), an organic nonlinear optical (NLO) material for frequency conversion was grown by slow evaporation solution growth technique at room temperature has been reported. The compound was prepared by Stockman method of benzoylation. The solubility curve shows linear nature up to a temperature of 313 K. XRD study reveals that the crystal belongs to monoclinic system with P21 non-centrosymmetric space group. The fundamental vibrational frequency of various functional groups (400-4000 cm-1) in the crystal was determined from FTIR analysis. 1H and 13C NMR spectral studies reveal the presence of proton and carbon network in the grown crystalline sample. The optical behaviour of the crystal was ascertained by optical UV absorption spectral studies. The UV cut off region (λmax) lies around 200 nm and the crystal is absolutely transparent from 220–800 nm suggesting its application as NLO material. The thermal stability of the crystal was determined by thermogravimetric and differential thermal analyses. Laser damage threshold of BV was found to be 0.34 GW/cm2 and hence BV can be used in frequency doubler system. Photoconductivity study of BV revealed negative photoconductiviting nature of the sample. The microhardness studies confirm that BV has a moderate Vickers hardness number (VHN) value in comparison to the other organic NLO crystals.

This paper presents a novel class of nonlinear optical (NLO) polymer for second harmonic generation (SHG). This new class of NLO polymer consists of the linear polyurethane, T-polymer, of tolylene 2,4-diisocyanate (TDI) with 3-[(2-hydroxyethyl)amino]-5-(hydroxymethyl)-4‘-nitroazobenzene (T-AZODIOL), whose dipole moment is aligned transverse to the main chain backbone. For comparison, the linear polyurethane L-polymer, whose NLO chromophore is incorporated into the main chain, is synthesized from TDI with 4-[N-(2-hydroxyethyl)-N-methylamino]-3‘-(hydroxymethyl)azobenzene (AZODIOL). T-polymer poled at optimum conditions of a corona poling voltage 8.0 kV, a temperature of 95 °C, and a time of 60 min shows a large second-order nonlinearity of d33 = 1.6 × 10-7 esu (67 pm/V) with good thermal stability at room temperature. The oriented NLO dipole moments for T-polymer do not show significant relaxation at ambient conditions after 60 days except for small depression a few days after poling, whereas, the SHG activity of L-polymer is largely decayed at room temperature. The better thermal stability of this new class of T-polymer is related to the smaller free volume in T-polymer.

Nonlinear optical (NLO) polymers have been considered promising materials for wavelength conversion at a low pump power. However, they have not been readily adopted to practical applications due to their high absorption coefficients, especially at a shorter interacting wavelength. Our theoretical analysis proves that the influence of absorption coefficients can be mitigated significantly in cascaded wavelength conversion (CWC) processes. According to our example study, maximum conversion efficiencies for CWC can compare even with those for second-harmonic generation in many NLO polymers. Thus CWC can become a pertinent application of NLO polymers. However, to obtain such efficient CWC, several realistic problems should be resolved in practical devices.

Crystal growth is an important branch of solid state physics and material science. The Growth of Nonlinear Optical (NLO) materials crystals receives much importance nowadays because NLO materials have various applications in modern technologies like Laser technology, optoelectronics, and fiber optics, etc. Potassium dihydrogen phosphate (KDP) is a well known nonlinear optical (NLO) material with different applications. Since most of the amino acids exhibit NLO property, it is of interest to dope them in KDP. In the present study, amino acid L-Phenylalanine doped KDP crystals have been grown by slow evaporation solution growth technique. In present study powder XRD analysis was carried out which show that pure and L-Phenylalanine doped KDP crystals have tetragonal symmetry. The doping of L-Phenylalanine was confirmed by FT-IR and paper chromatography. Thermal analysis has been performed on the grown crystals.The SHG efficiency of L-Phenylalanine doped KDP crystals was found to be increasing with a doping concentration of L-Phenylalanine. Introduction. The demand for high quality large size KDP single crystal increases due to its application as frequency conversion crystal in inertial confinement fusion [1, 2]. KDP belongs to scalenohedral (twelve faced) class of tetragonal crystal system [3]. With the aim of improving the second harmonic generation (SHG) efficiency of KDP, researchers have attempted to modify KDP crystals by doping different types of impurities. The non-linear optical (NLO) and other properties of the crystal have been improved by doping of organic impurities [4-9]. KDP doped with amino acids like L-glutamine acid, L-gistidine, and L-valine was reported [10]. Kumaresan et al. [11] has reported the thermal dielectric properties of amino acids such as L-glutamic acid, L-histidine and L-valine doped KDP crystals. They found improved NLO properties of the KDP crystal and modifications in the structural, optical, mechanical, and electrical properties, too. Parikh [12] has reported the SHG efficiency of L-arginine doped KDP crystal. Kumaresan et al. [13] has also reported the effect of metal ion and amino acid doping on the optical properties of KDP crystal. Muley et al. [5] has studied thermal, NLO properties of KDP crystal doped with L-arginine and L-alanine. Suresh Kumar and Rajendrababu [6] studied the effects of L-arginine, L-histidine and glycine on the growth of KDP single crystals and observed that addition of amino acid enhances transparency, thermal stability and NLO efficiency of KDP crystals. Amino acid family crystals are playing an important role in the field of non-linear optical organic molecular crystal. Among them L-Phenylalanine (LPA) with chemical formula (C6H5CH2CH(NH2)COOH) is the α-amino acid with a non-reactive hydrophobic benzyl side chain. The physical, chemical and non-linear optical properties of KDP are enhanced by adding optically active amino acids as dopants.The growth and characterization of Single crystals of KDP doped with amino acids namely glycine, arginine, alanine, tryptophan, histidine have been reported earlier [5-8]. In the present work, single crystals of Potassium dihydrogen phosphate (KDP) added

Defect engineering of second-harmonic generation in nonlinear optical semiconductors

Crosslinkable benzocyclobutene based host polymer for high temporal stability of organic second-order nonlinear optical materials

We have synthesized and evaluated nonlinear optical (NLO) properties of azo dye attached novel NLO polymers with high optical nonlinearity and/or high thermal stability. An azo-dye attached NLO polymer with a furan derivative as an acceptor was synthesized. The second order NLO susceptibility (χ(2) 33) at 1.3 μm fundamental wavelength was more than two times larger than that of the NLO polymer with dicyanovinyl (DCV) acceptor and the same azobenzene structure. A χ (2) 33 of 43pm/V was obtained. Polymethacrylic acid reacted with a typical azo dye, Disperse Red 1 dye (DR-1), in its side-chain was also synthesized using a new approach, i.e., via intermediate reaction of the acid and N,N'- dicyclohexylcarbodiimide. Glass transition temperatures Tg of 170°C were obtained for the dye attached polymethacrylic acid with the DR- 1 contents of 29 mol%. A χ (2) 33 of 53pm/V at 1.3 μm was obtained. This polymer can be further improved to have more stablility by heat treatment. Through this treatment, the methacryl imide structure was formed and the polymer has Tg of 165°C. This imidized polymer exhibited a χ (2) 33 of 45 pm/V at 1.3 μm and maintained about 90% of its initial value after 230 hours or more at 100°C. Novel NLO polyarylethers where electron-withdrawing groups for NLO activity were introduced into the polymers by post-functionalization were developed. These NLO polyarylethers have high Tgs, typically higher than 200°C. A 100 mol% DR-1 dye containing NLO polymer with the fluorene structure has very low optical propagation loss of 0.42dB/cm at 1.3 μm wavelength and shows low polarized light dependence of the refractive indices. The polymer has χ (2) 33 of about 57pm/V at 1.3|um fundamental wavelength and the nonlinearity was maintained at 100°C for more than 200 hrs Key words: second order nonlinear optics, nonlinear optical polymers, thermal stability, furan derivative, polymethacrylic acid, azo dye, imidization, polyarylether

The current study employed a novel approach to design polymer composites with modified structural and declined optical band gaps. The results obtained in the present work for polymer composites can be considered an original method to make a new field for research based on green chemistry. Natural dyes extracted from green tea were mixed with hydrated zinc acetate (Zn(CH3COO)2·2H2O) to produce a metal complex. FTIR results comprehensively established the formation of the Zn-metal complex. The interaction among various components of PVA : Zn-metal complex composite was investigated using FTIR spectroscopy. The non-existence of anion bands of acetate in the Zn-metal complex spectrum confirms the formation of the Zn-metal complex. XRD analysis reveals that the Zn-metal complex improves the amorphous phase of the PVA-based composites. The absorption edge of the doped films shifted towards the lower photon energies. Optical dielectric properties were used to determine N/m*, ε∞, τ, μopt, ωp, and ρopt; the W–D model was used to calculate Ed, Eo and no parameters. The optical dielectric loss parameter was used to determine the optical band gap while the Tauc model was employed to identify various types of electron transitions. The optical energy band gap was 6.05 eV for clean PVA while it decreased to 1 eV for PVA inserted with the Zn-metal complex. The increase in Urbach energy from 0.26 eV to 0.45 eV is an evidence of the boost of amorphous phases in PVA : Zn-metal complex composites. The nonlinear refractive index and the first-order and second-order nonlinear optical susceptibilities were determined. The value of Eo obtained from the W–D model closely matches the optical energy band gap obtained from the Tauc model, which indicates the precision of the analysis in the present study. The increase in SELF and VELF in the composite films establishes that new energy states assigned to the added Zn-metal complex amplify the probability of light–matter interaction.

A hot topic in materials science is to search for nonlinear optical (NLO) crystals, which are indispensable in current laser technology, future optical information, and precision measurements. In the period of the 1980s and 1990s, the anionic group theory proposed by Prof. Chuangtian Chen has greatly promoted the inventions of BaB2O4 (BBO), LiB3O5 (LBO), and KBe2BO3F2 (KBBF) which are widely applied in the ultraviolet (UV) spectral region today. From the beginning of this century, the rapid development of laser science and technology urgently demands new NLO crystals for wider application ranges. However, commercial NLO crystals in deep-UV and mid-infrared (mid-IR) regions are scarce. The challenge arises from the stringent criteria at various wavelengths and inefficient exploration strategy. As such, more comprehensive and quantitative theoretical guidance is necessary to improve and supplement the NLO structure-property understandings. Benefiting from high-performance computing resources, first-principles design and simulations came into being, which is more applicable to the understanding of mid-IR NLO mechanism and suitable for the efficient design of new NLO structures for current needs. In the past decade, a complete set of computational research programs based on first-principles simulations have been developed, which have promoted the development of NLO crystals in the deep-UV and mid-IR regions, and guided the subsequent and further experimental explorations. Based on our developed first-principles materials design system, the discoveries of NLO materials have ranged from basic theoretical design to rapid-prototyping and final experimental synthesis. In this Account, we will concisely summarize our ab initio guided and forward-looking studies on NLO crystals, which are our original contributions to this field and can be consulted by other material fields. First, we will review the development of NLO crystals and the important features of NLO materials. Second, we will summarize the important role of computer-aided design in advancing the NLO material field and our developed NLO material design system based on the first-principles simulations. Third, we will introduce the first-principles design for new deep-UV NLO crystals using two novel design proposals, i.e., interlayer cationic replacement and intralayer anionic substitution. Meanwhile, we will illustrate the hierarchical molecular engineering optimizations for mid-IR NLO crystals by illustrating an extended mid-IR NLO family pedigree, from which many promising mid-IR NLO systems were predicted theoretically and confirmed experimentally. Finally, we will give an outlook to explore new functional NLO crystals guided by our first-principles design and simulations. We believe that the computer-assisted exploration for new functional NLO materials is useful for understanding structure-property relationships and can provide researchers with a new approach to cost-effective and data-driven materials design.