New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Investigations on the structural, optical and magnetic properties of nanostructured cerium oxide in pure and doped forms and its polymer nanocomposites

In recent years, nanoscience and nanotechnology has emerged as one of the most important and exciting frontier areas of research interest in almost all fields of science and technology. This technology provides the path of many breakthrough changes in the near future in many areas of advanced technological applications. Nanotechnology is an interdisciplinary area of research and development. The advent of nanotechnology in the modern times and the beginning of its systematic study can be thought of to have begun with a lecture by the famous physicist Richard Feynman. In 1960 he presented a visionary and prophetic lecture at the meeting of the American Physical Society entitled “there is plenty of room at the bottom” where he speculated on the possibility and potential of nanosized materials. Synthesis of nanomaterials and nanostructures are the essential aspects of nanotechnology. Studies on new physical properties and applications of nanomaterials are possible only when materials are made available with desired size, morphology, crystal structure and chemical composition. Cerium oxide (ceria) is one of the important functional materials with high mechanical strength, thermal stability, excellent optical properties, appreciable oxygen ion conductivity and oxygen storage capacity. Ceria finds a variety of applications in mechanical polishing of microelectronic devices, as catalysts for three-way automatic exhaust systems and as additives in ceramics and phosphors. The doped ceria usually has enhanced catalytic and electrical properties, which depend on a series of factors such as the particle size, the structural characteristics, morphology etc. Ceria based solid solutions have been widely identified as promising electrolytes for intermediate temperature solid oxide fuel cells (SOFC). The success of many promising device technologies depends on the suitable powder synthesis techniques. The challenge for introducing new nanopowder synthesis techniques is to preserve high material quality while attaining the desired composition. The method adopted should give reproducible powder properties, high yield and must be time and energy effective. The use of a variety of new materials in many technological applications has been realized through the use of thin films of these materials. Thus the development of any new material will have good application potential if it can be deposited in thin film form with the same properties. The advantageous properties of thin films include the possibility of tailoring the properties according to film thickness, small mass of the materials involved and high surface to volume ratio. The synthesis of polymer nanocomposites is an integral aspect of polymer nanotechnology. By inserting the nanometric inorganic compounds, the properties of polymers can be improved and this has a lot of applications depending upon the inorganic filler material present in the polymer.

Ultrasonic measurement of the elastic properties of benzoyl glycine single crystals

Certain organic crystals are found to possess high non- linear optical coefficients,often one to two orders of magnitude higher than those of the well known inorganic non-linear optical materials.Benzoyl glycine is one such crystal whose optical second-harmonic generation efficiency is much higher than that of potassium dihydrogen phosphate. Single crystals of benzoyl glycine are grown by solvent evaporation technique using N,N-dimethyl formamide as the solvent.All the nine second-order elastic stiffness constants of this orthorhombic crystal are determined from ultrasonic wave velocity measurements employing the pulse echo overlap technique.The anisotropy of elastic wave propagation in this crystal is demonstrated by plotting the phase velocity, slowness,Young's modulus and linear compressibility surfaces along symmetry planes.The volume compressibility, bulk modulus and relevant Poisson's ratios are also determined. Variation of the diagonal elastic stiffness constants with temperature over a limited range are measured and reported.

Photoacoustic and photothermal deflection studies on certain selected photonic materials“

The emergence of lasers in the early sixties has not only revolutionized the field of optics and communication but also paved new ways in the field of material characterization. Material studies using photothermal techniques possess certain unique characteristics and advantages over conventional methods. The most important aspect of photothennal techniques is their ability to perform noncontact and nondestructive measurement. Photoacoustics, photothermal deflection, thermal lens, photothermal radiometry and photopyroelectric methods are some of the commonly used and powerful techniques for the thermal and optical characterization of materials using lasers. In this thesis the applications of photoacoustic and photothermal deflection techniques for the thermal and optical characterization of different photonic materials, namely, semiconductors, liquid crystals and dye-doped polymers are discussed

Effect of II‐VI Semiconductor Nanomaterials and Electron Irradiation on Polystyrene (PS) & Poly(ethylene‐co‐vinyl acetate) (EVA)

Organic-inorganic nanocomposites combine unique properties of both the constituents in one material. Among this group of materials, clay based as well as ZnO, TiO2 nanocomposites have been found to have diverse applications. Optoelectronic devices require polymerinorganic systems to meet certain desired properties. Dielectric properties of conventional polymers like poly(ethylene-co-vinyl acetate) (EVA) and polystyrene (PS) may also be tailor tuned with the incorporation of inorganic fillers in very small amounts. Electrical conductivity and surface resistivity of polymer matrices are found to improve with inorganic nanofillers. II-VI semiconductors and their nano materials have attracted material scientists because of their unique optical properties of photoluminescence, UV photodetection and light induced conductivity. Cadmium selenide (CdSe), zinc selenide (ZnSe) and zinc oxide (ZnO) are some of the most promising members of the IIVI semiconductor family, used in light-emitting diodes, nanosensors, non-linear optical (NLO) absorption etc. EVA and PS materials were selected as the matrices in the present study because they are commercially used polymers and have not been the subject of research for opto-electronic properties with semiconductor nanomaterials

Characterization of radio frequency plasma using Langmuir probe and optical emission spectroscopy

The radio frequency plasma generated during the sputtering of Indium Tin Oxide target using Argon was analyzed by Langmuir probe and optical-emission spectroscopy. The basic plasma parameters such as electron temperature and ion density were evaluated. These studies were carried out by varying the RF power from 20 to 50 W. A linear increase in ion density and an exponential decrease in electron temperature with rf power were observed. The measured plasma parameters were then correlated with the properties of ITO thin films deposited under similar plasma conditions.

Fabrication and Characterization of All-Fiber Components for Optical Access Networks

This Thesis deals with the fabrication and characterization of novel all-fiber components for access networks. All fiber components offer distinctive advantages due to low forward and backward losses, epoxy free optical path and high power handling. A novel fabrication method for monolithic 1x4 couplers, which are vital components in distributed passive optical networks, is realized. The fabrication method differs from conventional structures with a symmetric coupling profile and hence offers ultra wideband performance and easy process control. New structure for 1x4 couplers, by fusing five fibers is proposed to achieve high uniformity, which gives equivalent uniformity performance to 1x4 planar lightwave splitters, isolation in fused fiber WDM is improved with integration of long period gratings. Packaging techniques of fused couplers are analyzed for long term stability.

Optical and Thermal Characterization of Dye Intercalated Montmorillonites and Rare Earth Doped Materials

Nondestructive photothermal methods as well as optical absorption and fluorescence spectroscopy are utilized to characterise three different materials, both thermally and optically. The possibility of using montmorillonite clay minerals, after textile waste-water treatment, is investigated for further applications. The laser induced luminescence studies and thermal characterisation of certain rare earth titanates prepared by self propagating high temperature synthesis method are also presented. Moreover, effort is made to characterise rare earth doped sol gel silica glasses with the help of these nondestructive techniques.

Characterization of rhodamine 6G doped polymer optical fiber by side illumination fluorescence

The length-dependent tuning of the fluorescence spectra of a dye doped polymer fiber is reported. The fiber is pumped sideways and the fluorescence is measured from one of the ends. The excitation of a finite length of dye doped fiber is done by a diode pumped solid state laser at a wavelength of 532 nm. The fluorescence emission is measured at various positions of the fiber starting from a position closer to the pumping region and then progressing toward the other end of the fiber. We observe that the optical loss coefficients for shorter and longer distances of propagation through the dye doped fiber are different. At longer distances of propagation, a decrease in optical loss coefficient is observed. The fluorescence peaks exhibit a redshift of 12 nm from 589 to 610 nm as the point of illumination progresses toward the detector end. This is attributed to the self-absorption and re-emission of the laser dye in the fiber.

Fabrication and characterization of dye-doped polymer optical fiber as a light amplifier

The fabrication and characterization of a Rhodamine 6G-doped polymer optical fiber amplifier have been carried out. Two different schemes were employed to characterize the optical fiber: the stripe illumination technique to study the fiber as a gain medium and another technique to study its performance as an amplifier. We observed a spectral narrowing from 42 to 7 nm when the pump energy was increased to 6 mJ in the stripe illumination geometry. A gain of 18 dB was obtained in the amplifier configuration. The effects of pump power and dye concentration on the performance of the fiber as an amplifier were also studied.

Fabrication and characterization of dye mixture doped polymer optical fiber as a broad wavelength optical amplifier

Rhodamine 6G and Rhodamine B dye mixture doped polymer optical fiber amplifier (POFA), which can operate in a broad wavelength region (60 nm), has been successfully fabricated and tested. Tunable operation of the amplifier over a broad wavelength region is achieved by mixing different ratios of the dyes. The dye doped POFA is pumped axially using 532 nm, 10 ns laser pulses from a frequency doubled Q-switched Nd: YAG laser and the signals are taken from an optical parametric oscillator. A maximum gain of 22.3 dB at 617 nm wavelength has been obtained for a 7 cm long dye mixture doped POFA. The effects of pump energy and length of the fiber on the performance of the fiber amplifier are also studied. There exists an optimum length for which the amplifier gain is at a maximum value.

Fluorescence characterization and gain studies on a dye-doped graded index polymer optical-fiber preform

Preparation of an appropriate optical-fiber preform is vital for the fabrication of graded-index polymer optical fibers (GIPOF), which are considered to be a good choice for providing inexpensive high bandwidth data links, for local area networks and telecommunication applications. Recent development of the interfacial gel polymerization technique has caused a dramatic reduction in the total attenuation in GIPOF, and this is one of the potential methods to prepare fiber preforms for the fabrication of dye-doped polymer-fiber amplifiers. In this paper, the preparation of a dye-doped graded-index poly(methyl methacrylate) (PMMA) rod by the interfacial gel polymerization method using a PMMA tube is reported. An organic compound of high-refractive index, viz., diphenyl phthalate (DPP), was used to obtain a graded-index distribution, and Rhodamine B (Rh B), was used to dope the PMMA rod. The refractive index profile of the rod was measured using an interferometric technique and the index exponent was estimated. The single pass gain of the rod was measured at a pump wavelength of 532 nm. The extent of doping of the Rh B in the preform was studied by axially exciting a thin slice of the rod with white light and measuring the spatial variation of the fluorescence intensity across the sample.

Linear and nonlinear optical characteristics of ZnO-SiO2 nanocomposites.

We present the spectral and nonlinear optical properties of ZnO-SiO2 nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed, and the strongest UV emission of a typical ZnO-SiO2 nanocomposite is over three times stronger than that of pure ZnO. The nonlinearity of the silica colloid is low, and its nonlinear response can be improved by making composites with ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absorption and nonlinear scattering. The nonlinear refractive index and the nonlinear absorption increase with increasing ZnO volume fraction and can be attributed to the enhancement of exciton oscillator strength. ZnO-SiO2 is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

“Fabrication and characterization of polymer optical fibers for photonic device applications

Although the main application of optical fibers are in the field of telecommunication, optical fiber based sensors of various designs are becoming valuable devices for wide industrial applications. The advantages of optical fiber-based sensors include high sensitivity, insensitivity to electromagnetic radiation; spark free, light weight and minimal intrusiveness due to their relatively small size and deployment in harsh and hostile environments. It has been proved that POI-7 based sensors can be employed to detect a great variety of parameters including temperature, humidity, pressure, refractive index etc. The proposed thesis presented in six chapters deals with the work carried on dye doped and undoped POF for photonic device applications such as amplifier, laser and sensor