Synthesis and Characterization of Some Organic Semiconductors and Investigations on the Effect of Swift Heavy Ions on Their Properties

In this work polymers belonging to polyaniline and polyaniline doped with camphor sulphonic acid are synthesised. Cobalt phthalocyanine is an interesting candidate belonging to the tetramers. Studies on the composites containing cobalt phthalocyanine tetramer and polyaniline doped with camphor sulphonic acid for various concentration are also undertaken in order to understand the mechanism. RF plasma polymerised aniline and furfural are prepared. The structural and electrical properties are evaluated. The bombardment of swift heavy ions of these films are carried out and the effect of irradiation on their properties is also investigated.

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

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers” submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.