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

Novel Strategies for Heterocyclic Constructions via 1, 4-Dipolar Intermediates

In the thesis entitled " Novel Strategies for Heterocyclic Constructions via 1 ,4-Dipolar Intermediates"Synthesis of a complex organic molecules essentially involves the formation of carbon-carbon and carbon-heteroatom bonds. Various synthetic methods are available for these processes involving ionic, pericyclic and radical reactions. Among the pericyclic reactions, dipolar cycloaddition reactions, introduced by Huisgen, have emerged as a very powerful tool for heterocyclic construction. Heterocyclic compounds remain an important class of organic molecules due to their natural abundance and remarkable biological activity, thus constituting an intergral part of pharmaceutical industry. In this respect, developing newer synthetic methodology for heterocyclic construction has been an area of immense interest. In recent years, 1,3-dipolar cycloaddition reactions proved to be efficient routes to a wide variety of five membered heterocycles, as attested by their application in the total synthesis of various complex organic molecules. However, the potential application of similar 1,4- dipolar cycloaddition reactions for the construction of six memebered heterocycles remained underexploited. In this context, a systematic investigation of the reactivity of 1,4-dipoles generated from nitrogen heterocycles (pyridine and its analogues) and dimethyl acetylenedicarboxy!ate (DMAD) towards various dipolarophiles has been carried out and the results are embodied.

Investigations on the Dynamics of Combination Maps and the Analysis of Bifurcation in a Discontinuous Logistic Map

This thesis is a study of discrete nonlinear systems represented by one dimensional mappings.As one dimensional interative maps represent Poincarre sections of higher dimensional flows,they offer a convenient means to understand the dynamical evolution of many physical systems.It highlighting the basic ideas of deterministic chaos.Qualitative and quantitative measures for the detection and characterization of chaos in nonlinear systems are discussed.Some simple mathematical models exhibiting chaos are presented.The bifurcation scenario and the possible routes to chaos are explained.It present the results of the numerical computational of the Lyapunov exponents (λ) of one dimensional maps.This thesis focuses on the results obtained by our investigations on combinations maps,scaling behaviour of the Lyapunov characteristic exponents of one dimensional maps and the nature of bifurcations in a discontinous logistic map.It gives a review of the major routes to chaos in dissipative systems,namely, Period-doubling ,Intermittency and Crises.This study gives a theoretical understanding of the route to chaos in discontinous systems.A detailed analysis of the dynamics of a discontinous logistic map is carried out, both analytically and numerically ,to understand the route it follows to chaos.The present analysis deals only with the case of the discontinuity parameter applied to the right half of the interval of mapping.A detailed analysis for the n –furcations of various periodicities can be made and a more general theory for the map with discontinuities applied at different positions can be on a similar footing

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Studies on some Metal Complexes of Dithio Ligands

The thesis deals with our studies on the synthesis and elucidation of structure of some metal complexes of dithio ligands, such as the dithiocarbamates, xanthates and 2-aminocyclopent-1-ene-1-dithiocarboxylate and its N-alkyl derivatives.2-Aminocyclopent-1-ene-1-dithiocarboxylate (ACDA) is an interesting ligand, because of its potential dual capability of bonding between the metal and the ligand. Since the earlier reports on the complexes of ACDA contain contradictory ideas on the nature of its bonding, it was thought worthwhile to undertake a detailed and systematic study of these type of complexes. As the ACDA complexes have very low solubilities in solvents like chloroform, we have used the isopropyl derivative of ACDA as the ligand. The increased solubility of these complexes have made it possible to investigate their NMR and solution electronic spectra.The complexes of this ligand have not yet been reported in the literature.We have synthesised some new mixed ligand complexes of dithiocarbamates by reacting bis(dithiocarbamato)-µ-dichloro dicopper complexes (obtained by the reaction of mixed benzoic dithiocarbamic anhydride and copper(II) chloride) with ACDA or its N-alkyl derivatives.Interactions of metal halides with the mixed anhydrides formed from benzoylchloride and xanthates have also been investigated. Novel complexes of the type, [Cu2(RXant)CI] (R=i-Bu, i-Pr, n-Bu or n-Pr)) have been isolated from the reaction of copper(II) chloride and the mixed anhydride, and these reactions appear to be like the clock reactions reported in the literature.It also deal with the characterisation of the complexes of the type [Hg(R2d t c )X] (X=Cl, Br or 1),[Cu3(R2dtc)6][Cu2Br6] and [Cu(R2dtc)Cl2](R2=Me2,Et2,Pip,Morph or Pyrr)respectively, synthesised by simple and novel routes, different from those reported earlier.

NANO - ZINC OXIDE: A Novel Modifier for Thermoplastics

Various synthesis routes have been developed in recent years for the preparation of nanoparticles. One of those methods is polymer induced crystallization. The first objective of the present work was to prepare nano ZnO powder by polymer induced crystallization in chitosan solution and to characterize the material using different techniques like TEM, SEM, XRD, FTLR, UV spectroscopy, TGA, DSC etc.The second object of the study is to prepare composites using nano ZnO. It has been undertaken to explore the potential of nano ZnO as reinforcement in engineering as well as commodity thermoplastics to widen their application spectra. We selected three engineering thermoplastics like [poly ethylene terephthalate, polyamide 6, and polycarbonate] and three commodity plastics like [polypropylene, high density polyethylene, and polystyrene] for the study. To date one of the few disadvantages associated with nanoparticle incorporation has concerned toughness and impact performance. Modification of polymers could reduce impact performance. The present study also focused on whether nano ZnO can act as a modifier for thennoplastics, without sacrificing their impact strength.

Fabrication and Characterization of Chalcogenide nano composite based materials for Photonic device applications

In this context,in search of new materials based on chalcogenide glasses,we have developed a novel technique for fabrication of chalcogenide nano composites which are presented in this theis.The techniques includes the dissolution of bulk chalcogenide glasses in amine solvent.This solution casting method allows to retain the attractive optical properties of chalcogenide glasses enabling new fabrication routes for realization of large area thick-thin films with less cost. Chalcogenide glass fiber geometry opens new possibilities for a large number of applications in optics,like remote temperature measurements ,CO2 laser power delivery, and optical sensing and single mode propagation of IR light.We have fabricated new optical polymer fibers doped with chalcogenide glasses which can be used for many optical applications.The present thesis also describes the structural,thermal and optical characterization of certain chalocogenide based materials prepared for different methods and its applications.

2(3H)-Furanones and related substrates: Synthetic strategies and selectivity profile in their reactivity

The synthesis and reactions of simple derivatives of 2(3H)- and 3(2H)furanones have attracted considerable attention in recent years, primarily in connection with development of routes to antitumor agents that contain this ring as central structural unit. They also serve as useful synthetic building blocks for lactones and furans and are the precursors of a wide variety of biologically important heterocyclic systems. Although a number of syntheses of furanones were known they were in many cases limited to specific substitution pattems. The development of altemative strategies for the preparation of these heterocycles is therefore of considerable importance or continues to be a challenge.We propose to develop new and general approaches to the synthesis of furanone ring systems from simple and readily available starting materials since we were interested in examining their rich photochemistry. The photochemical reactivity of Beta,gama-unsaturated lactams and lactones is a subject of current interest. Some of the prominent photoreaction pathways of unsaturated lactones include decarbonylation, solvent addition to double bonds, decarboxylation, migration of aryl substituents and dimerisation. lt was reported earlier that the critical requirement for clean photochemical cleavage of the acyl-oxygen bond is the presence ofa double bond adjacent to the ether oxygen and 2(3H)-furanones possessing this structural requirement undergo facile decarbonylation. But related phenanthrofuranones are isolated as photostable end products upon irradiation. Hence we propose to synthesis a few phenanthro-2(3H)-furanones to study the effect of a radical stabilising group at 3-position of furanone ring on photolysis. To explore the tripletmediated transformations of 2(3H)-furanones in polar and nonpolar solvents a few 3,3-bis(4-chlorophenyl)-5-aryl-3H-furan-2-ones and 3,3-di(p-tolyl)-5-aryl- 3H-furan-2-ones were synthesised from the corresponding dibenzoylstyrene precursors by neat thermolysis. Our aim was to study the nature of intermediates involved in these transformations.We also explored the possibility of developing a new and general approach to the synthesis of 3(2H)-furanones from simple and readily available starting materials since such general procedures are not available. The protocol developed by us employs readily available phenanthrenequinone and various 4-substituted acetophenones as starting materials and provides easy access to the required 3(2H)-furanone targets. These furanone derivatives have immense potential for further investigations .We also aimed the synthesis of a few dibenzoylalkene-type systems such as acenaphthenone-2—ylidene ketones and phenanthrenone-9-ylidene ketones. These systems were expected to undergo thermal rearrangement to give furanones and spirofuranones. Also these systems can be categorised as quinonemethides which are valuable synthetic intermediates.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Physicochemical and Biochemical Characterization of Enzymes Immobilized on lnorganic Matrices

Biotechnology is currently considered as a useful altemative to conventional process technology in industrial and catalytic fields. The increasing awareness of the need to create green and sustainable production processes in all fields of chemistry has stimulated materials scientists to search for innovative catalysts supports. lmmobilization of enzymes in inorganic matrices is very useful in practical applications due to the preserved stability and catalytic activity of the immobilized enzymes under extreme conditions. Nanostructured inorganic, organic or hybrid organic-inorganic nanocomposites present paramount advantages to facilitate integration and miniaturization of the devices (nanotechnologies), thus affording a direct connection between the inorganic, organic and biological worlds. These properties, combined with good chemical stability, make them competent candidates for designed biocatalysts, protein-separation devices, drug delivery systems, and biosensors Aluininosilicate clays and layered double hydroxides, displaying, respectively, cation and anion exchange properties, were found to be attractive materials for immobilization because of their hydrophilic, swelling and porosity properties, as well as their mechanical and thermal stability.The aim of this study is the replacement of inorganic catalysts by immobilized lipases to obtain purer and healthier products.Mesocellular silica foams were synthesized by oil-in-water microemulsion templating route and were functionalized with silane and glutaraldehyde. " The experimental results from IR spectroscopy and elemental analysis demonstrated the presence of immobilized lipase and also functionalisation with silane and glutaraldehyde on the supports.The present work is a comprehensive study on enzymatic synthesis of butyl isobutyrate through esterification reaction using lipase immobilized onto mesocellular siliceous foams and montmorillonite K-10 via adsorption and covalent binding. Moreover, the irnrnobil-ization does not modify the nature of the kinetic mechanism proposed which is of the Bi-Bi Ping—Pong type with inhibition by n-butanol. The immobilized biocatalyst can be commercially exploited for the synthesis of other short chain flavor esters. Mesocellular silica foams (MCF) were synthesized by microemusion templating method via two different routes (hydrothermal and room temperature). and were functionalized with silane and glutaraldehyde. Candida rugosa lipase was adsorbed onto MCF silica and clay using heptane as the coupling medium for reactions in non-aqueous media. I From XRD results, a slight broadening and lowering of d spacing values after immobilization and modification was observed in the case of MCF 160 and MCF35 but there was no change in the d-spacing in the case of K-10 which showed that the enzymes are adsorbed only on the external surface. This was further confirmed from the nitrogen adsorption measurements

Studies on the universal parameters and onset of chaos in dissipative systems

It has become clear over the last few years that many deterministic dynamical systems described by simple but nonlinear equations with only a few variables can behave in an irregular or random fashion. This phenomenon, commonly called deterministic chaos, is essentially due to the fact that we cannot deal with infinitely precise numbers. In these systems trajectories emerging from nearby initial conditions diverge exponentially as time evolves)and therefore)any small error in the initial measurement spreads with time considerably, leading to unpredictable and chaotic behaviour The thesis work is mainly centered on the asymptotic behaviour of nonlinear and nonintegrable dissipative dynamical systems. It is found that completely deterministic nonlinear differential equations describing such systems can exhibit random or chaotic behaviour. Theoretical studies on this chaotic behaviour can enhance our understanding of various phenomena such as turbulence, nonlinear electronic circuits, erratic behaviour of heart and brain, fundamental molecular reactions involving DNA, meteorological phenomena, fluctuations in the cost of materials and so on. Chaos is studied mainly under two different approaches - the nature of the onset of chaos and the statistical description of the chaotic state.

“Law on Transboundary Movement of Hazardous Substances through Sea

This study pertain to legal control of pollution from transboundary movement of hazardous substances through sea. It is an emerging area in international maritime law. There is growing environmental awareness that oceans are no longer an inexhaustible resource. This has resulted in a complex system of integrated ocean policies and international legal frame work in this regard. Considering the peculiar nature of hazardous substances, the development of law in this regard has been haphazard. The legal framework in this area is not comprehensive and lacks coherence. India is geo-strategically located in the central part of Indian Ocean through which many international sea routes lie. India is also fast emerging as a maritime hub. Indian legal framework in this respect also suffers from serious pitfalls. In this backdrop, this study makes a sincere attempt to identify and analyse the legal intricacies in this area, in order to evolve a better regime for control of pollution pursuant to transboundary movement of hazardous substances through sea

Studies On Developing A Facile Route For The Synthesis Of Highly Substituted Quinoline And Indole Derivatives

the thesis entitled “STUDIES ON DEVELOPING A FACILE ROUTE FOR THE SYNTHESIS OF HIGHLY SUBSTITUTED QUINOLINE AND INDOLE DERIVATIVES” portrays our attempt to revisit the mechanism of 1,3- dipolar additions with a view to establishing whether it follows a concerted pathway or a stepwise reaction sequence through the formation of a zwitterionic intermediate, which will definitely contribute to the better use of this technique. Furthermore, we propose to develop novel routes for the synthesis of quinoline and indole derivatives with predefined substitution pattern. The thesis is devided into four chapters

On the magnetic properties of ultra-Þne zinc ferrites

Zinc ferrite belongs to the class of normal spinels where it is assumed to have a cation distribution of Zn2`(Fe3`)2(O2~)4, and it is purported to be showing zero net magnetisation. However, there have been recent reports suggesting that zinc ferrite exhibits anomaly in its magnetisation. Zinc ferrite samples have been prepared by two di¤erent routes and have been analysed using low energy ion scattering, Mo¬ ssbauer spectroscopy and magnetic measurements. The results indicate that zinc occupies octahedral sites, contrary to the earlier belief that zinc occupies only the tetrahedral sites in a normal spinel. The amount of zinc on the B site increases with decrease in particle size. The LEIS results together with the Mo¬ ssbauer results and the magnetic measurements lead to the conclusion that zinc occupies the B site and the magnetisation exhibited by ultraÞne particles of zinc is due to short range ordering