Third-order Nonlinear Optical Applications Research Articles

Crystal growth, structural, Hirshfeld surface analysis, optical and laser damage threshold analysis of 2-Methylimidazolium glutarate single crystal: third-order nonlinear optical applications

Crystal growth, structural, Hirshfeld surface analysis, optical and laser damage threshold analysis of 2-Methylimidazolium glutarate single crystal: third-order nonlinear optical applications

A comprehensive assessment on synthesis, growth, theoretical & optical properties of glycine zinc sulphate pentahydrate single crystal for third-order nonlinear optical applications

A comprehensive assessment on synthesis, growth, theoretical & optical properties of glycine zinc sulphate pentahydrate single crystal for third-order nonlinear optical applications

DFT-based study of the impact of transition metal coordination on the charge transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol

ABSTRACTTheoretical investigations of the impact of transition metal chelation on the electron/hole-transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol (L) are reported herein. Calculations were carried out via density functional theory (DFT)-based methods, employing exchange–correlation functionals and basis sets of different qualities. Results have shown that free L is a moderate electron/hole-transporter, but that its Pd(II) and Pt(II) complexes are excellent hole- and electron-transport materials respectively, owing to their very small reorganisation energies and relatively large electronic coupling matrix elements or transfer integrals. These results indicate that the complexes are potentially suitable charge transport materials for the construction of organic light emitting diodes (OLEDs). Nevertheless, the results also revealed a higher NLO activity for L than its metal complexes. Interestingly, the first and second hyperpolarizabilities, along with some computed NLO properties of both L and its complexes are found to be remarkably higher than those of the prototypical push–pull molecule, para-nitroaniline. Accordingly, these compounds are potential candidates for the fabrication of optoelectronic and photonic devices for second- and third-order NLO applications. Summarily, metal chelation is found to enhance the charge transport properties in some cases, and to slightly diminish NLO response of L in all cases investigated.

Growth and characterization of dl-Mandelic acid (C6H5CH(OH)CO2H) single crystal for third-order nonlinear optical applications

An organic conjugated chromophore dl-mandelic acid (DLMA) single crystal was synthesized and grown-up by means of slow evaporation technique. Single crystal X-ray diffraction study proclaimed that the DLMA crystal crystallized in monoclinic system with centrosymmetric space group P21/c. The various characteristic fundamental vibration frequencies were identified by FTIR spectroscopic studies. UV–visible spectral analysis concluded that the lower cut-off wavelength and calculated direct optical band gap of DLMA as 257 nm and 5.40 eV respectively. Thermal property of dl-mandelic acid was established through thermogravimetric and differential scanning calorimetric technique. The electric field response of DLMA crystal was investigated from the dielectric studies at a few selected temperatures and frequencies. The quantum chemical assessments such as HOMO-LUMO, molecular electrostatic potential and NLO activity were calculated and presented. In order to determine mechanical strength of DLMA crystal for various loads using Vickers microhardness tester. The real and imaginary parts of the third-order susceptibility (χ3) were evaluated with the Z-scan technique using closed and open signatures respectively and was found to be Re (χ3) = 4.15 × 10−6 esu and Im (χ3) = 0.47 × 10−6 esu.

Third-Harmonic Scattering for Fast and Sensitive Screening of the Second Hyperpolarizability in Solution.

Organic materials are promising candidates for integration in optical network components allowing fast communication. Ultimate speeds can be obtained by exploiting third-order nonlinear optical light-matter interactions that ultimately rely on the molecular second hyperpolarizability (γ). The exploration of molecular structure-property relations is crucial to optimize γ but requires state of the art measurement techniques which are both sensitive and efficient. Unfortunately, present-day methods for probing the performance of third-order nonlinear optical (NLO) materials fail to meet at least one of those requirements. We have developed third-harmonic scattering (THS) as an alternative method to measure γ in solution, featuring a simple experimental setup and straightforward data analysis. Since the signal strength relies on |γ|2, the method proves to be very sensitive and allows rapid screening of organic molecules in dilute solutions for potential use in third-order NLO applications. In this manuscript, we demonstrate the experimental procedure and calibration of THS and have determined the second hyperpolarizability |γ| of commonly used solvents, which can be used as an internal calibration standard. As a proof of concept we determined γ of trans-stilbene and found it to be in excellent agreement with values obtained by other techniques.

Synthesis, growth, structure and characterization of 1-Ethyl-2-(2-p-tolyl-vinyl)-pyridinium iodide (TASI) – An efficient material for third-order nonlinear optical applications

A new organic stilbazolium derivative, 1-Ethyl-2-(2-p-tolyl-vinyl)-pyridinium iodide (TASI), was grown from methanol:acetonitrile (1:3) mixed solvent by slow evaporation technique. Single crystal X-ray diffraction analysis revealed that TASI crystallizes in triclinic system with a centrosymmetric space group P-1. The molecular structure and the presence of expected functional groups of TASI were confirmed by 1H NMR and FT-IR spectroscopic studies. The HOMO and LUMO energies influence the charge transfer takes place within the molecule. The grown crystal was thermally stable up to 210 °C as determined by TG/DTA analysis. UV-Vis-NIR spectral study showed that the grown crystal was transparent in the wavelength range of 438–1100 nm. Mechanical behaviour and surface laser damage threshold were studied to find the suitability of the grown crystal for device fabrication. Studies of its third-order nonlinear optical properties using a Z-scan technique demonstrates that TASI crystal is capable of exhibiting reverse saturable absorption and self-focusing performance with the second-order molecular hyperpolarizability (γ) 4.983 × 10−34 esu. The third-order nonlinear susceptibility of TASI was found to be 8.931 × 10−6 esu, which is higher than a few other stilbazolium derivative crystals.

Investigation on the crystal growth, molecular structure and nonlinear optical susceptibilities of 2-[2-(4-Ethoxy-phenyl)-vinyl]-1-ethyl-stilbazolium iodide (EESI) by Z-scan technique using He–Ne laser for third-order nonlinear optical applications

Organic 2-[2-(4-Ethoxy-phenyl)-vinyl]-1-ethyl-stilbazolium iodide (EESI), a derivative of the stilbazolium family single crystal was synthesized by condensation method. Nearly perfect as-gown single crystals of EESI structure was confirmed by single-crystal X-ray diffraction studies. The crystal has a triclinic system with the space group P-1, the molecule consists of one pyridinium cation, one iodide anion, and 0·5H2O molecules. The nature of charge transfer, molecular properties, electrostatic potential map, and HOMO-LUMO energy gap of EESI have been theoretically investigated by Sparton’10 V1.0.1 program. The optical transparency of EESI was studied by Uv–Visible spectral analysis. The growth features were observed during the etching studies using a Carl Zeiss optical microscope (50X magnification). The mechanical behavior of the crystal was estimated by Vickers microhardness test, which shows reverse indentation size effect (RISE) with good mechanical stability. Both the dielectric constant and dielectric loss increases with the increasing temperature and attain almost constant at higher frequencies, which justify the crystal quality and essential parameter for electro-optic device applications. The complex impedance analysis explains the electrical property of EESI. TGA and DTA measurements determined the thermal stability of the grown crystal. Laser-induced damage threshold energy measurements exhibit that the excellent resistance with good threshold energy up to 2.08GW/cm2 that was found to be more than that of some known organic and inorganic NLO crystals. Photoconductivity of EESI crystal confirms that the positive photoconductivity nature. Also, the third-order nonlinear optical (NLO) properties of EESI were investigated by using the single beam Z-scan technique under the Visible light (632.8nm) region. The results show that EESI has effective third-order nonlinear optical property with the nonlinear refractive index n2 =1.787×10-11m2/W, third-order nonlinear optical susceptibility χ(3) =4.229×10-6esu and second-order hyperpolarizability (γ) =1.468×10–33 esu. It is found to be larger than that of some organic NLO materials. All the obtained results are making it a potential candidate as useful non-linear optical (NLO) applications.

Pyrene-Based Small Molecular Nonlinear Optical Materials Modified by ‘‘Click-Reaction’’

Two pyrene derivatives were successfully synthesized via an efficient copper(I)-catalyzed azide alkyne 1,3-dipolar cycloaddition. The photophysical and electrochemical properties were characterized using ultraviolet-visible absorption spectra, fluorescence spectra, cyclic voltammograms and density functional theory modulations. These results showed that the symmetry structure of these derivatives formed an electron-delocalized organic system, which have larger effects in achieving a third-order nonlinear optical (NLO) response. The third-order nonlinear properties including the nonlinear absorption and the nonlinear susceptibilities investigated by Z-scan technique indicate that the title compounds can serve as a promising candidate for third-order NLO applications.

Studies on the growth, spectral, structural, electrical, optical and mechanical properties of Uronium 3-carboxy-4-hydroxybenzenesulfonate single crystal for third-order nonlinear optical applications

Organic Uronium 3-carboxy-4-hydroxybenzenesulfonate (UCHBS) nonlinear optical single crystal was grown by solution growth technique. The solubility and nucleation studies were performed for UCHBS at different temperatures 30, 35, 40, 45, 50 and 55°C. The crystal structure of UCHBS was elucidated from single crystal X-ray diffraction study. High resolution X-ray diffraction technique was employed to study the perfection and internal defects of UCHBS crystal. Infrared and Raman spectra were recorded to analyze the vibrational behavior of chemical bonds and its functional groups. The physico-chemical changes, stability and decomposition stages of the UCHBS compound were established by TG–DTA studies. The dielectric phenomenon of UCHBS crystal was studied at different temperatures with respect to frequency. Linear optical properties of transmittance, cut-off wavelength, band gap of UCHBS were found from UV–visible spectral studies. Third-order nonlinear optical susceptibility, nonlinear refractive index, nonlinear optical absorption coefficient values were measured by Z-scan technique. The mechanical properties of UCHBS crystal was studied by using Vicker’s microhardness test. The growth features of UCHBS crystal were analyzed from etching studies.

Synthesis and third-order nonlinear optical properties of low band gap 3,4-ethylenedioxythiophene–quinoxaline copolymers

A series of low band gap 3,4-ethylenedioxythiophene (EDOT) and quinoxaline donor–acceptor (D–A) copolymers were designed and their electronic structure and properties were investigated by employing density functional theory in the periodic boundary condition using HSE06 exchange correlation functional and 6-31G basis set. The acceptors investigated were acenaphthylene, phenyl and phenanthrene substituted quinoxaline units. DFT calculations have been performed for both monomers and model oligomers to analyse their electronic properties. The designed copolymers have been synthesized through a simple and facile method. i.e., direct arylation reaction. The photophysical and electrochemical properties of EDOT–quinoxaline copolymers were investigated. The copolymers, P(EDOT-ACEQX), P(EDOT-BZQX), and P(EDOT-PHQX) exhibited theoretical band gap of 1.81, 1.76 and 1.63eV, respectively using the DFT/HSE06/6-31G calculation and the optical band gap of 1.80, 1.75, and 1.66eV, respectively, according to the onset edge of lower energy peak of the polymers in solution. Electrochemical studies demonstrated that quinoxaline moieties elevated the HOMO (highest occupied molecular orbital) level and lowered the LUMO (lowest unoccupied molecular orbital) level of the PEDOT (Poly(3,4-ethylenedioxythiophene)) backbone. The theoretical and experimental evaluations revealed the regular alternation of quinoxaline moieties. The band gap of the copolymers was well correlated with the acceptor strength. The experimental results supported the theoretical predictions. The third-order nonlinear optical (NLO) properties of D–A EDOT–quinoxaline copolymers, evaluated by z-scan method with nanosecond laser beam at 532nm, are reported. Polymers possess strong refractive effect with nonlinear refraction coefficient of −0.47×10−10, −0.95×10−10 and −0.64×10−10esu, respectively. Effective third-order nonlinear susceptibilities were calculated to be 0.82×10−11, 1.46×10−11 and 1.17×10−11esu, respectively. Polymers showed good optical limiting behavior due to two photon absorption (TPA). The results suggest that EDOT–quinoxaline copolymers are promising materials for third-order nonlinear optical applications.

Growth and characterization of hydroxyethylammonium picrate single crystals for third-order nonlinear optical applications

A centrosymmetric crystal structure has been determined by single crystal X-ray diffraction analysis of Hydroxyethylammonium Picrate (HEAP) crystals. It is mentioned for the first time in the literature for its monoclinic structure crystallizing in centrosymmetrical space group P21/c which is basically a donor acceptor organic material grown by slow evaporation solution growth technique. We used Fourier Transform Infra Red and Raman spectroscopy to study the intermolecular interactions present in the 1:1 combination of picric acid and ethanolamine. Optical, mechanical and thermal stabilities of the title crystal were carried out to propose the material for useful applications. Z-scan is used to measure the effective third-order nonlinear optical susceptibility, which is found to be 3.24 × 10−3 esu. The negative sign of the nonlinear refractive index n2 = −9.2 × 10−5 cm2 W−1, indicates that this material exhibits self-defocusing optical nonlinearity. We also report the details of theoretical studies of the macroscopic nonlinear optical properties and molecular orbital calculations by quantum chemical calculations.

Dioxaborine- and Indole-Terminated Polymethines: Effects of Bridge Substitution on Absorption Spectra and Third-Order Polarizabilities

Cyanine-like dyes are promising candidates for third-order nonlinear optical (NLO) applications such as all-optical switching. Here, we examine the consequences for linear and nonlinear optical properties of varying substituents on the central methine unit of bis(dioxaborine)-terminated anionic pentamethines and bis(indole)-terminated cationic heptamethines. The variation in absorption maxima and electrochemical potentials with structure can generally be rationalized using the Dewar-Knott rules, providing that mesomeric and inductive electron-withdrawal and donation are explicitly considered. In the case of nitro- and (dioxaborinyl)vinyl-substituted bis(dioxaborine) pentamethines, the low-energy transitions are significantly broadened, consistent with (1)H NMR spectra indicating deviation from cyanine-like geometry. Real and imaginary parts of the third-order polarizabilities, Re(γ) and Im(γ), were measured at 1.3 μm. The values of Im(γ) indicate that the values of Re(γ) are significantly resonantly enhanced, while the positive value of Re(γ) found for a nitro-substituted dioxaborine example is atypical for a symmetrical polymethine and suggests that a two-state treatment is inadequate. The relevance of these results to chromophore design for third-order NLO applications is discussed.

Synthesis, growth and characterization of a third-order nonlinear optical crystal based on the borate ester with sodium supporting its structural framework

A novel third-order nonlinear optical (NLO) crystal based on the organic borate carboxylate ester, with formula [Na4(H2O)5][B{O2CCH(O)Ph}2]4 (abbreviated as LMBNa), has been prepared in aqueous solution. Single-crystal X-ray diffraction analysis reveals that the boron atom is coordinated with two L-mandelic ligands by alkoxide and carboxylate groups, forming the [B{OOCCH(O)C6H5}]− anion. The sodium cation supports its structural framework of borate anions in the formation of a cross-linked structure. Bulk single crystals of LMBNa were grown from acetonitrile/water by the temperature lowering method. Studies of its third-order NLO properties using a Z-scan technique demonstrate that the LMBNa crystal possesses a strong saturable absorption and the self-focusing effect. Its second molecular hyperpolarizability (γ) at 532 nm is calculated to be (3.9 ± 0.2) × 10−31 esu. Furthermore, dielectric experiments reveal that LMBNa has a quite low-dielectric constant (∼3.43) and shows an anisotropy of frequency dependence along the different crystallographic directions. Such dielectric behaviors will favor the application of the LMBNa crystal under the electric field. All the results indicate that LMBNa might be a potential candidate material for the third-order NLO applications.

ChemInform Abstract: Nonlinear Optical Materials

The current state of materials development in nonlinear optics is summarized, and the promise of these materials is critically evaluated. Properties and important materials constants of current commercial materials and of new, promising, inorganic and organic molecular and polymeric materials with potential in second- and third-order nonlinear optical applications are presented.

3,3′-Benzene-1,4-diylbis[1-(substituted)phenylprop-2-en-1-one] derivatives: A new class of materials for third-order nonlinear optical applications

We have investigated the third-order nonlinear optical parameters of Bischalcones embedded in DMF solution and in solid PMMA matrix, by Z-scan technique using nanosecond laser pulse trains at 532 nm. Z-scan results reveal that the Bischalcones exhibits negative nonlinear refractive index as high as 10 −11 esu. The molecular two-photon absorption cross-section σ 2 ′ of Bischalcones were of the order 10 −46 cm 4 s/photon, which is nearly two orders of magnitude larger than that of Rhodamine 6G which is 10 −48 – 10 −50 cm 4 s/photon. We found that, the two-photon absorption (TPA) is the dominating nonlinear process leading to nonlinear absorption in both the cases in solution and as well as in solid medium. Based on TPA process, the Bischalcones exhibit good optical power limiting of nanosecond laser pulses at the input wavelength. The nonlinear optical parameters found to increase on enhancing the strength of the electron donor groups indicating the dependence and importance of electron donor/acceptor units on third-order nonlinear optical susceptibility χ (3).

6, 6 -distyryl-3, 3 -bipyridine derivatives: a novel class of tunable chromophores for second-and third-order nonlinear optical applications

We report on the design, synthesis, structural characterization and quadratic as well as cubic nonlinear optical (NLO) properties of a series of organic chromophores (6,6'-distyryl-3,3'-bipyridine derivatives disubstituted with donor (D) and/or acceptor (A) end-groups). The compounds are either dipolar (push–pull molecules) or apolar (symmetric D–A–A–D molecules). By lateral substitutions of the π-conjugated bridge and by varying the nature of the donor/acceptor (D/A) pair, we were able to tune both the mesogenic and NLO properties of the chromophores. Their second-order NLO properties were evaluated by the electric-field-induced second-harmonic technique. All the compounds are transparent at the second-harmonic wavelength of typical laser sources (1.32 and 1.55 μm). For the mesogenic chromophores, first hyperpolarizabilities extrapolated to infinite wavelength, β0, between 16 and 85 × 10−30 esu were measured. These compounds exhibit enhanced hyperpolarizabilities compared to typical NLO liquid crystal chromophores reported in the literature. Both the nonlinear refractive index n2 and the two-photon absorption (TPA) coefficient α2 were simultaneously measured at λ = 1064 nm, using a single-shot (50 ps, 10 Hz) multi-channel Z-scan method. For all molecular compounds, Z-scan measurements in dichloromethane solutions show a large nonlinear refractive index, close to that of pure carbon disulfide, without detectable TPA in most cases. These measurements lead to extrapolated nonresonant n2 values between 1 × 10−16 and 4 × 10−16 m2 W−1, whatever the electronic structure of the compounds. Hence, apolar symmetric D–A–A–D molecules appear to be an interesting novel family of NLO dyes.

Ferrocenyl derivatives with Mo(Tp An) units for second- and third-order nonlinear optical applications

New molecular systems based on donor/acceptor organometallic groups connected by π-conjugated bridges have been designed and their nonlinear optical (NLO) properties investigated. At macroscopic level SHG and THG responses were measured on corona-poled spin-coated films and at molecular level cubic hyperpolarizability data were obtained from solution. For comparison related compounds having NO 2 as acceptor group were also analyzed. New trends have been derived from the analysis of the molecular characteristics: nature of the acceptor and structural variations on the bridge.

A New Method to Synthesize Unsymmetrical Dithiolene Metal Complexes of 1,3-Dithiole-2-thione-4,5-dithiolate for Third-Order Nonlinear Optical Applications

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTA New Method to Synthesize Unsymmetrical Dithiolene Metal Complexes of 1,3-Dithiole-2-thione-4,5-dithiolate for Third-Order Nonlinear Optical ApplicationsJie Dai, Guo-Qing Bian, Xin Wang, Qing-Feng Xu, Min-Yan Zhou, Megumu Munakata, Masahiko Maekawa, Ming-Hong Tong, Zhen-Rong Sun, and He-Ping ZengView Author Information Department of Chemistry, Suzhou University Suzhou 215006, P.R. China Department of Chemistry, Kinki University Kowakae, Higashi-Osaka 577-8502, Japan Laboratory for Quantum Optics Department of Physics East China Normal University Shanghai, 200062, P.R. China Cite this: J. Am. Chem. Soc. 2000, 122, 44, 11007–11008Publication Date (Web):October 21, 2000Publication History Received5 June 2000Revised7 September 2000Published online21 October 2000Published inissue 1 November 2000https://doi.org/10.1021/ja001976eCopyright © 2000 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views696Altmetric-Citations62LEARN 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 InReddit Read OnlinePDF (31 KB) Get e-AlertsSupporting Info (2)»Supporting Information Supporting Information SUBJECTS:Lasers,Ligands,Metals,Nonlinear optics,Optical properties Get e-Alerts

Synthesis and Properties of Novel Crosslinkable Phthalocyanine Monomers

Polymer films incorporating phthalocyanine rings are useful for third-order nonlinear optical applications. Two axially modified silicon phthalocyanine monomers containing crosslinkable sites have been synthesized. A monomer containing acrylate groups was crosslinked thermally whereas a monomer containing cinnamate groups was crosslinked both thermally and photochemically. Both monomers can be made into solid polymeric films incorporating over 20% (w/w) of the phthalocyanine ring with no observable phase segregation. Elemental analysis, 1H NMR, FT-IR, and UV-Vis spectroscopy were employed for the structural characterization of the monomers. The kinetics of crosslinking such as reaction conversion versus time and temperature, heat of reaction (ΔH), activation energy (ΔE) and reaction order (n), and the thermal properties of the crosslinked films have also been investigated.

Preparation, properties and crystal structures of new nickel(II) complexes of 1,2-asymmetrically substituted dithiolenes for third-order non-linear optical applications

Three new nickel(II) complexes of 1-alkyl-2-phenyl asymmetrically substituted dithiolenes [Ni(SCR1CR2S)2](R1= Ph; R2= Bun, cyclopentylmethyl or 4-pentylcyclohexyl) have been prepared and their electrochemical properties and near-IR spectra studied. The crystal structures of the complexes in which R2= Bun or cyclopentylmethyl have been determined. The presence of bulky substituents adjacent to the ring has no affect upon the electrochemical or near-infrared properties. Third-order non-linear optical coefficients were measured by degenerate four-wave mixing.