SYNTHESIS OF CROSS-LINKED 2ND-ORDER NONLINEAR-OPTICAL POLYMERS WITH HIGH T-G

Synthesis and characterization of a diamino dihydroxyl azo compound were reported, The crosslinking reaction process of the diamino dihydroxyl azo compound with the biuret of hexamethylene diisocyanate was studied by FTIR, The glass transition temperatures of crosslinked polymers were measured by DSC, The orientation and oriented stability of crosslinked and poled polymers were studied by UV-Vis spectra.

SYNTHESIS AND CHARACTERIZATION OF CROSS-LINKED 2ND-ORDER NONLINEAR-OPTICAL POLYMER

The present paper reports the synthesis of glycidyl monoether of 4-[(p-nitrophenyl) azo] phenol (GMNA) and crosslinking reaction of GMNA with hexamethylene diisocyanate biuret (HDIB). The Tg of crosslinked polymer was investigated by DSC. The orientation and stability of the poled and crosslinked polymer film were studied by UV-Vis spectra and Maker fringe method.

High speed nonlinear optical components for next-generation optical communications

Electronic signal processing systems currently employed at core internet routers require huge amounts of power to operate and they may be unable to continue to satisfy consumer demand for more bandwidth without an inordinate increase in cost, size and/or energy consumption. Optical signal processing techniques may be deployed in next-generation optical networks for simple tasks such as wavelength conversion, demultiplexing and format conversion at high speed (≥100Gb.s-1) to alleviate the pressure on existing core router infrastructure. To implement optical signal processing functionalities, it is necessary to exploit the nonlinear optical properties of suitable materials such as III-V semiconductor compounds, silicon, periodically-poled lithium niobate (PPLN), highly nonlinear fibre (HNLF) or chalcogenide glasses. However, nonlinear optical (NLO) components such as semiconductor optical amplifiers (SOAs), electroabsorption modulators (EAMs) and silicon nanowires are the most promising candidates as all-optical switching elements vis-à-vis ease of integration, device footprint and energy consumption. This PhD thesis presents the amplitude and phase dynamics in a range of device configurations containing SOAs, EAMs and/or silicon nanowires to support the design of all optical switching elements for deployment in next-generation optical networks. Time-resolved pump-probe spectroscopy using pulses with a pulse width of 3ps from mode-locked laser sources was utilized to accurately measure the carrier dynamics in the device(s) under test. The research work into four main topics: (a) a long SOA, (b) the concatenated SOA-EAMSOA (CSES) configuration, (c) silicon nanowires embedded in SU8 polymer and (d) a custom epitaxy design EAM with fast carrier sweepout dynamics. The principal aim was to identify the optimum operation conditions for each of these NLO device configurations to enhance their switching capability and to assess their potential for various optical signal processing functionalities. All of the NLO device configurations investigated in this thesis are compact and suitable for monolithic and/or hybrid integration.

Control of the orientational order and nonlinear optical response of the "push-pull" chromophore RuPZn via specific incorporation into densely packed monolayer ensembles of an amphiphilic four-helix bundle peptide: characterization of the peptide-chromophore complexes.

"Push-pull" chromophores based on extended pi-electron systems have been designed to exhibit exceptionally large molecular hyperpolarizabilities. We have engineered an amphiphilic four-helix bundle peptide to vectorially incorporate such hyperpolarizable chromophores having a metalloporphyrin moiety, with high specificity into the interior core of the bundle. The amphiphilic exterior of the bundle facilitates the formation of densely packed monolayer ensembles of the vectorially oriented peptide-chromophore complexes at the liquid-gas interface. Chemical specificity designed into the ends of the bundle facilitates the subsequent covalent attachment of these monolayer ensembles onto the surface of an inorganic substrate. In this article, we describe the structural characterization of these monolayer ensembles at each stage of their fabrication for one such peptide-chromophore complex designated as AP0-RuPZn. In the accompanying article, we describe the characterization of their macroscopic nonlinear optical properties.

Experimental characterization of the nonlinear optical and magneto-optical properties of interfaces

An effective ellipsometric technique to determine parameters that characterize second-harmonic optical and magneto-optical effects in centrosymmetric media within the electric-dipole approximation is proposed and outlined in detail. The parameters, which are ratios of components of the nonlinear-surface-susceptibility tensors, are obtained from experimental data related to the state of polarization of the second-harmonic-generated radiation as a function of the angle between the plane of incidence and the polarization plane of the incident, linearly polarized, fundamental radiation. Experimental details of the technique are described. A corresponding theoretical model is given as an example for a single isotropic surface assuming polycrystalline samples. The surfaces of air-Au and air-Ni (in magnetized and demagnetized states) have been investigated ex situ in ambient air, and the results are presented. A nonlinear, least-squares-minimization fitting procedure between experimental data and theoretical formulas has been shown to yield realistic, unambiguous results for the ratios corresponding to each of the above materials. Independent methods for verifying the validity of the fitting parameters are also presented. The influence of temporal variations at the surfaces on the state of polarization (due to adsorption, contamination, or oxidation) is also illustrated for the demagnetized air-Ni surface. (C) 2005 Optical Society of America

Performance of polarisation functionals for linear and nonlinear optical properties of bulk zinc chalcogenides ZnX (X=S,Se,Te).

We calculated the frequency dependent macroscopic dielectric function and second-harmonic generation of cubic ZnS, ZnSe and ZnTe within time-dependent density-polarisation functional theory. The macroscopic dielectric function is calculated in a linear response framework, and second-harmonic generation in a real-time framework. The macroscopic exchange–correlation electric field that enters the time-dependent Kohn–Sham equations and accounts for long range correlation is approximated as a simple polarisation functional αP, where P is the macroscopic polarisation. Expressions for α are taken from the recent literature. The performance of the resulting approximations for the exchange–correlation electric field is analysed by comparing the theoretical spectra with experimental results and results obtained at the levels of the independent particle approximation and the random-phase approximation. For the dielectric function we also compare with state-of-the art calculations at the level of the Bethe–Salpeter equation.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Ultrasonic measurement of the elastic constants of selected nonlinear optical /semiorganic crystals with orthorhombic symmetry

Ultrasonic is a good tool to investigate the elastic properties of crystals. It enables one to determine all the elastic constants, Poisson’s ratios, volume compressibility and bulk modulus of crystals from velocity measurements. It also enables one to demonstrate the anisotropy of elastic properties by plotting sections of the surfaces of phase velocity, slowness, group velocity, Young’s modulus and linear compressibility along the a-b, b-c and a-c planes. They also help one to understand more about phonon amplification and help to interpret various phenomena associated with ultrasonic wave propagation, thermal conductivity, phonon transport etc. Study of nonlinear optical crystals is very important from an application point of view. Hundreds of new NLO materials are synthesized to meet the requirements for various applications. Inorganic, organic and organometallic or semiorganic classes of compounds have been studied for several reasons. Semiorganic compounds have some advantages over their inorganic and inorganic counterparts with regard to their mechanical properties. High damage resistance, high melting point, good transparency and non-hygroscopy are some of the basic requirements for a material to be suitable for device fabrication. New NLO materials are being synthesized and investigation of the mechanical and elastic properties of these crystals is very important to test the suitability of these materials for technological applications

Spectral and nonlinear optical characterization of ZnO nanocomposites

The spectral and nonlinear optical characteristics of nano ZnO and its composites are investigated. The fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength and there is a red shift in emission peak with excitation wavelength. Apart from the observation of the reported ultra violet and green emissions, our results reveal that additional blue emissions at 420 nm and 490 nm are developed with increasing particle size. Systematic studies on nano ZnO have indicated the presence of luminescence due to excitonic emissions when excited with 255 nm as well as significant contribution from surface defect states when excited with 325 nm. In the weak confinement regime, the third-order optical susceptibility χ(3) increases with increasing particle size (R) and annealing temperature (T) and a R2 and T2.5 dependence of χ(3) is obtained for nano ZnO. ZnO nanocolloids exhibit induced absorption whereas the self assembled films of ZnO exhibit saturable absorption due to saturation of linear absorption of ZnO defect states and electronic effects. ZnO nanocomposites exhibit negative nonlinear index of refraction which can be attributed to two photon absorption followed by weak free carrier absorption. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. The nonlinear response of ZnO nanocomposites is wavelength dependent and switching from induced absorption to saturable absorption has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an optical limiter. ZnO based nanocomposites are potential materials for enhanced and tunable light emission and for the development of nonlinear optical devices with a relatively small optical limiting threshold.

Luminescence tuning and enhanced nonlinear optical properties of nanocomposites of ZnO–TiO2

In this article we present the spectral and nonlinear optical properties of ZnO–TiO2 nanocomposites prepared by colloidal chemical synthesis. Emission peaks of ZnO–TiO2 nanocomposites change from 340 nm to 385 nm almost in proportion to changes in Eg. The nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour. The nonlinear refractive index and the nonlinear absorption increase with increasing TiO2 volume fraction at 532 nm and can be attributed to the enhancement of exciton oscillator strength. ZnO–TiO2 is a potential nanocomposite material for the tunable light emission and for the development of nonlinear optical devices with a relatively small limiting threshold