Studies on Photosensitive polymers for Optical Recording

Department of Polymer Science and Rubber Technology,Cochin University of Science and Technology

Studies on Conducting Polymers and Conductive Elastomer Composites

The primary aim of this work has been to develop conductive silicone and nitrile rubbers, which are extensively used for making conductive pads in telephone sets, calculators and other applications. Another objective of the work has been to synthesise and characterize novel conducting polymers based on glyoxal and paraphenylenediamine- poly(p-phenylenediazomethine. Conducting polymer matrices were developed from polymer blends such as poly(pphenylenediazomethine), polyethylene, PVC and silica and their properties were studied.

Investigations on some selected conducting polymers and polymer composites for possible optoelectronic applications

Department of Physics, Cochin University of Science and Technology

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection is detected using a position sensitive detector and its output is fed to a lock-in-amplifIer from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

Amorphous Oxide Transparent Thin Films: Growth, Characterisation and Application to Thin Film Transistors

This work mainly concentrate to understand the optical and electrical properties of amorphous zinc tin oxide and amorphous zinc indium tin oxide thin films for TFT applications. Amorphous materials are promising in achieving better device performance on temperature sensitive substrates compared to polycrystalline materials. Most of these amorphous oxides are multicomponent and as such there exists the need for an optimized chemical composition. For this we have to make individual targets with required chemical composition to use it in conventional thin film deposition techniques like PLD and sputtering. Instead, if we use separate targets for each of the cationic element and if separately control the power during the simultaneous sputtering process, then we can change the chemical composition by simply adjusting the sputtering power. This is what is done in co-sputtering technique. Eventhough there had some reports about thin film deposition using this technique, there was no reports about the use of this technique in TFT fabrication until very recent time. Hence in this work, co-sputtering has performed as a major technique for thin film deposition and TFT fabrication. PLD were also performed as it is a relatively new technique and allows the use high oxygen pressure during deposition. This helps to control the carrier density in the channel and also favours the smooth film surface. Both these properties are crucial in TFT.Zinc tin oxide material is interesting in the sense that it does not contain costly indium. Eventhough some works were already reported in ZTO based TFTs, there was no systematic study about ZTO thin film's various optoelectronic properties from a TFT manufacturing perspective. Attempts have made to analyse the ZTO films prepared by PLD and co-sputtering. As more type of cations present in the film, chances are high to form an amorphous phase. Zinc indium tin oxide is studied as a multicomponent oxide material suitable for TFT fabrication.

Studies on Heat Diffusion in Selected Conducting Polymers using Probe Beam Deflection and Photoacoustic Techniques

In the present study, radio frequency plasma polymerization technique is used to prepare thin films of polyaniline, polypyrrole, poly N-methyl pyrrole and polythiophene. The thermal characterization of these films is carried out using transverse probe beam deflection method. Electrical conductivity and band gaps are also determined. The effect of iodine doping on electrical conductivity and the rate of heat diffusion is explored.Bulk samples of poyaniline and polypyrrole in powder form are synthesized by chemical route. Open photoacoustic cell configuration is employed for the thermal characterization of these samples. The effect of acid doping on heat diffusion in these bulk samples of polyaniline is also investigated. The variation of electrical conductivity of doped polyaniline and polypyrrole with temperature is also studied for drawing conclusion on the nature of conduction in these samples. In order to improve the processability of polyaniline and polypyrrole, these polymers are incorporated into a host matrix of poly vinyl chloride. Measurements of thermal diffusivity and electrical conductivity of these samples are carried out to investigate the variation of these quantities as a function of the content of polyvinyl chloride.

Novel Approaches to Biodegradable Polymers: Synthesis and Biodegradation Studies

Biodegradable polymers have opened an emerging area of great interest because they are the ultimate solution for the disposal problems of synthetic polymers used for short time applications in the environmental and biomedical field. The biodegradable polymers available until recently have a number of limitations in terms of strength and dimensional stability. Most of them have processing problems and are also very expensive. Recent developments in biodegradable polymers show that monomers and polymers obtained from renewable resources are important owing to their inherent biodegradability, biocompatibility and easy availability. The present study is, therefore, mostly concemed with the utilization of renewable resources by effecting chemical modification/copolymerization on existing synthetic polymers/natural polymers for introducing better biodegradability and material properties.The thesis describes multiple approaches in the design of new biodegradable polymers: (1) Chemical modification of an existing nonbiodegradable polymer, polyethylene, by anchoring monosaccharides after functionalization to introduce biodegradability. (2) Copolymerization of an existing biodegradable polymer, polylactide, with suitable monomers and/or polymers to tailor their properties to suit the emerging requirements such as (2a) graft copolymerization of lactide onto chitosan to get controlled solvation and biodegradability and (2b) copolymerization of polylactide with cycloaliphatic amide segments to improve upon the thermal properties and processability.

Amorphous Selenium films using CBD: A Novel Selenisation technique for preparing lndium Selenide and Copper lndium Selenide Thin Films

In the present work, we describe our efforts to develop device quality CuInSe2, films through low cost, simple and eco-friendly hybrid techniques. The most important point to be highlighted here is that the method fully avoids the use of poisonous gases such as H2Se/Se vapour. Instead, selenisation is achieved through solid state reaction between amorphous selenium and polycrystalline metal layers resulting in both binary and ternary selenides. Thin films of amorphous selenium (a-Se) used for this is deposited using Chemical Bath Deposition (CBD). CulnSe2 films are prepared through the selenisation process. Another PV material, indium selenide (In2Se3) thin films are also prepared using this process.

Functionalized Silicon Polymers: Novel Materials for Catalysis

Dept.of Applied Chemistry,Cochin University of Science and Technolgy

Design and Synthesis of Conjugated Polymers for Photovoltaic and Chemosensor Applications

Department of Applied Chemistry, Cochin University of Science and Technology

Electrical switching studies on the thin films of polyfuran and polyacrylonitrile prepared by plasma polymerisation and vacuum evaporated amorphous silicon

This thesis Entitled Electrical switching studies on the thin flims of polyfuran and polyacrylonitrile prepared by plasma polymerisation and vacuum evaporated amorphous silicon.A general introduction to the switching and allied phenomena is presented. Subsequently, developments of switching in thin films are described. The Mott transition is qualitatively presented. The working of a switching transitor is outlined and compared to the switching observed in thin films. Characteristic parameters of switching such as threshold voltage, time response to a, voltage pulse, and delay time are described. The various switching configurations commonly used are discussed. The mechanisms used to explain the switching behaviour like thermal, electrothermal and purely electronic are reviewed. Finally the scope, feasibility and the importance of polymer thin films in switching are highlighted.

Elecrical conduction and dielectric behaviour of thin films of vacuum evaporated amorphous silicon, hydrogenated amorphous silicon and chemically deposited cadmium sulphide

A brief account of the several methods used for the production of thin films is presented in this Chapter. The discussions stress on the important methods used for the fabrication of a-si:H thin films. This review' also reveals ‘that almost all the general methods, like vacuum evaporation, sputtering, glow discharge and even chemical methods are currently employed for the production of a-Si:H thin films. Each method has its own advantages and disadvantages. However, certain methods are generally preferred. Subsequently a detailed account of the method used here for the preparation of amorphous silicon thin films and their hydrogenation is presented. The metal chamber used for the electrical and dielectric measurements is also described. A brief mention is made-on the electrode structure, film area and film geometry.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Photoacoustic investigation of the optical and thermal properties of selected amorphous chalcogenide semiconductors

This thesis work has mainly concentrated on the investigation of the ,optical and thermal properties of binary semiconducting chalcogenide glasses belonging to the AivB¥5x and AZBXEX families. The technique used for these studies is a relatively new one namely, the photoacoustic (PA) technique. This technique is based on the detection of acoustic signal produced in an enclosed volume when the sample is irradiated by an intensity modulated radiation. The signal produced depends upon the optical properties of the sample, and the thermal properties of the sample, backing material and the surrounding gas. For the present studies an efficient signal beam gas-microphone PA spectrometer, consisting of a high power Xenon lamp, monochromator, light beam chopper, PA cell with microphone and lock-in amplifier, has been set up. Two PA cells have been fabricated: one for room temperature measurements and another for measurements at high temperatures. With the high temperature PA cell measurements can be taken upto 250°C. Provisions are incorporated. in both the cells to change the volume and to use different backing materials for the sample. The cells have been calibrated by measuring the frequency response of the cells using carbon black as the sample