Design, Fabrication and Characterization of Passive and Active Polymer Photonic Devices

The rapid developments in fields such as fibre optic communication engineering and integrated optical electronics have expanded the interest and have increased the expectations about guided wave optics, in which optical waveguides and optical fibres play a central role. The technology of guided wave photonics now plays a role in generating information (guided-wave sensors) and processing information (spectral analysis, analog-to-digital conversion and other optical communication schemes) in addition to its original application of transmitting information (fibre optic communication). Passive and active polymer devices have generated much research interest recently because of the versatility of the fabrication techniques and the potential applications in two important areas – short distant communication network and special functionality optical devices such as amplifiers, switches and sensors. Polymer optical waveguides and fibres are often designed to have large cores with 10-1000 micrometer diameter to facilitate easy connection and splicing. Large diameter polymer optical fibres being less fragile and vastly easier to work with than glass fibres, are attractive in sensing applications. Sensors using commercial plastic optical fibres are based on ideas already used in silica glass sensors, but exploiting the flexible and cost effective nature of the plastic optical fibre for harsh environments and throw-away sensors. In the field of Photonics, considerable attention is centering on the use of polymer waveguides and fibres, as they have a great potential to create all-optical devices. By attaching organic dyes to the polymer system we can incorporate a variety of optical functions. Organic dye doped polymer waveguides and fibres are potential candidates for solid state gain media. High power and high gain optical amplification in organic dye-doped polymer waveguide amplifier is possible due to extremely large emission cross sections of dyes. Also, an extensive choice of organic dye dopants is possible resulting in amplification covering a wide range in the visible region.

Studies on Soft Bycatch Reduction Devices for Selective Trawling

Trawling, though an efficient method of fishing, is known to be one of the most non-selective methods of fish capture. The bulk of the wild caught penaeid shrimps landed in India are caught by trawling.In addition to shrimps, the trawler fleet also catches considerable amount of non-shrimp resources. The term bycatch means that portion of the catch other than target species caught while fishing, which are either retained or discarded. Bycatch discards is a serious problem leading to the depletion of the resources and negative impacts on biodiversity. In order to minimize this problem, trawling has to be made more selective by incorporating Bycatch Reduction Devices (BRDs). There are several advantages in using BRDs in shrimp trawling. BRDs reduce the negative impacts of shrimp trawling on marine community. Fishers could benefit economically from higher catch value due to improved catch quality, shorter sorting time, lower fuel costs, and longer tow duration. Adoption of BRDs by fishers would forestall criticism by conservation groups against trawling.

Investigations on Hard Bycatch Reduction Devices for Selective Trawling

In the context of Indian fisheries there is a paucity of information on bycatch, in general, and bycatch reduction technologies, in particular. In this study, a detailed investigation on trawl bycatch and bycatch reduction measures is attempted with a view to evolve optimized BRDs for improving selectivity of commercial shrimp trawls. The objectives of the study included design and development of hard bycatch reduction devices (BRDs), comparative evaluation of hard bycatch reduction devices, for selective trawling, bycatch characterisation of the trawl landings, off Central Kerala; and investigations on status of the existing trawling systems operated off Central Kerala.

Low-voltage driven ZnS:Mn MIS and MISIM thin film electroluminescent devices with Eu2O3 insulator layer

AC thin film electroluminescent devices of MIS and MISIM have been fabricated with a novel dielectric layer of Eu2O3 as an insulator. The threshold voltage for light emission is found to depend strongly on the frequency of excitation source in these devices. These devices are fabricated with an active layer of ZnS:Mn and a novel dielectric layer of Eu2O3 as an insulator. The observed frequency dependence of brightness-voltage characteristics has been explained on the basis of the loss characteristic of the insulator layer. Changes in the threshold voltage and brightness with variation in emitting or insulating film thickness have been investigated in metal-insulator-semiconductor (MIS) structures. It has been found that the decrease in brightness occurring with decreasing ZnS layer thickness can be compensated by an increase in brightness obtained by reducing the insulator thickness. The optimal condition for low threshold voltage and higher stability has been shown to occur when the active layer to insulator thickness ratio lies between one and two.

Synthesis and Characterisation of Zinc Gallate Based Phosphors for Thin Film Electroluminescent Devices

Department of Physics, Cochin University of Science and Technology

Synthesis, Growth and Characterization of Oxide Phosphors for Thin Film Electroluminescent Devices

Department of Physics, Cochin University of Science and Technology

Fabrication and the study of zinc sulphide based electroluminescent devices

This thesis contains the author's work in preparing efficient EL phosphors, the details of fabrication of low voltage operated thin film EL (TFEL) devices and DC TFEL devices. Some of the important work presented here are related to the white light emitting ZnS:Cu,Pr,Cl phosphor which can be colour tuned by changing the excitation frequency, observation of energy transfer from Cu/Ag ions to rare earth ions in ZnS:(Cu/Ag), RE,Cl phosphors, development of TFEL device which can be operated below 50V, optimization of the device parameters for long life, high brightness in terms of the active and insulating layer thicknesses, observation of dependence of threshold voltage for the onset of emission on frequency of excitation when a novel dielectric Eu2O3 film was used as insulator and the devices with multicolor emission using ZnS doped with rare earth as active layer. Characterization based on other devices based on ZnS:Sm, ZnS:Pr, ZnS:Dy and their emission characteristics are also illustrated

Studies on electroluminescence using Powder and thin film devices

The subject of electroluminescence has currently acquired great importance because of its potential applications in display systems of a wide variety. A large number of scientists working in commercial, governmental as well as academic institutions all over the world are at present engaged in the intense effort to develop new and efficient phosphor materials and electroluminescent devices. This thesis presents the work carried out by the author in this field during the past few years. The studies discussed in this thesis are mostly confined to the development of some new phosphor materials, their uses in powder and thin film electroluminescent devices and to their electrical and spectral characteristics. Care has been taken to bring' out the physics involved in all the above aspects of the phenomenon

Blue, Green and Orange-Red Light Emitting Polymers: Synthesis, Characterization and Prospects of Applications in Optoelectronic Devices

Light emitting polymers (LEPs) are considered as the second generation of conducting polymers. A Prototype LEP device based on electroluminescence emission of poly(p-phenylenevinylene) (PPV) was first assembled in 1990. LEPs have progressed tremendously over the past 20 years. The development of new LEP derivatives are important because polymer light emitting diodes (PLEDs) can be used for the manufacture of next-generation displays and other optoelectronic applications such as lasers, photovoltaic cells and sensors. Under this circumstance, it is important to understand thermal, structural, morphological, electrochemical and photophysical characteristics of luminescent polymers. In this thesis the author synthesizes a series of light emitting polymers that can emit three primary colors (RGB) with high efficiency

Investigations on Metamaterial Based Spiral Inductors for Compact Microwave Devices

Division of Electronics Engineering

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

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 selected chalcogenide glasses towards the realization of photonic devices

Among various optical sensing schemes, infrared spectroscopy is a powerful tool for detecting and determining the composition of complex organic samples since vibrational finger prints of all biomolecules and organic species are located in this window. This spectroscopic technique is simple, reliable, fast, non-destructive, cost-effective while having low sensitivity. Use of metallic nanoparticles in association with a good IR transparent sensing substrate, is one of the promising solutions to enhance the sensitivity. Chalcogenide glasses are promising substrate material because of their extended optical transmission window starting from the visible to the far infrared range up to 20 μm, high refractive index usually between 2 and 3 and high optical nonlinearity, which make them good candidates as IR sensors and optical ultrafast nonlinear devices. These glasses are favorable sensor materials for the infrared spectral range because of their high IR transparency to allow for low optical loss at wavelengths corresponding to the characteristic optical absorption bands of organic molecules, high refractive index for tight confinement of optical energy within the resonator structure, processibility into thin film form, chemical compatibility for adhesion of silver nano particles and thin films and resistance to the chemical environment to be sensed. Molecules adsorbed to silver island structures shows enhanced IR absorption spectra and the extent of enhancement is determined by many factors such as the size, density and morphology of silver structures, optical and dielectric properties of the substrate material etc.