Micro- and nanostructuring of poly(ethylene-2,6-naphthalate) surfaces, for biomedical applications, using polymer replication techniques

Here we investigate the formation of superficial micro- and nanostructures in poly(ethylene-2,6-naphthalate) (PEN), with a view to their use in biomedical device applications, and compare its performance with a polymer commonly used for the fabrication of these devices, poly(methyl methacrylate) (PMMA). The PEN is found to replicate both micro- and nanostructures in its surface, albeit requiring more forceful replication conditions than PMMA, producing a slight increase in surface hydrophilicity. This ability to form micro/nanostructures, allied to biocompatibility and good optical transparency, suggests that PEN could be a useful material for production of, or for incorporation into, transparent devices for biomedical applications. Such devices will be able to be autoclaved, due to the polymer's high temperature stability, and will be useful for applications where forceful experimental conditions are required, due to a superior chemical resistance over PMMA.

Development of an optical redox chemical sensor for nitrite determination

An optical chemical sensor for the determination of nitrite based on incorporating methyltrioctylammonium chloride as an anionic exchanger on the triacetylcellulose polymer has been reported. The response of the sensor is based on the redox reaction between nitrite in aqueous solution and iodide adsorbed on sensing membrane using anion exchange phenomena. The sensing membrane reversibly responses to nitrite ion over the range of 6.52×10-6 - 8.70×10-5 mol L-1 with a detection limit of 6.05×10-7 mol L-1 (0.03 µg mL-1) and response time of 6 min. The relative standard deviation for eight replicate measurements of 8.70×10-6 and 4.34×10-5 mol L-1 of nitrite was 4.4 and 2.5 %, respectively. The sensor was successfully applied for determination of nitrite in food, saliva and water samples.

Methylene Blue Doped Polymers: efficient Media for Optical Recording

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8 and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Photosensitivity of Laser Dye Mixtures in Polymer Matrix – A Photoacoustic Study

Laser induced photoacoustic (PA) technique is used in the study of photostability of polymethyl methacrylate (PMMA) films doped with Rhodamine 6G -Rhodamine B dye system. Energy transfer from a donor molecule to an acceptor molecule in a dye mixture affects the output of the dye system. Details of investigations on the role of laser power, modulation frequency and the irradiation wavelength on the photosensitivity of the dye mixture doped PMMA films are presented.

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

Fabrication and Characterization of Dye Sensitized Polymer Films for Holographic Applications

Holographic technology is at the dawn of quick evolution in various new areas including holographic data storage, holographic optical elements, artificial intelligence, optical interconnects, optical correlators, commerce, medical practice, holographic weapon sight, night vision goggles and games etc. One of the major obstacles for the success of holographic technology to a large extent is the lack of suitable recording medium. Compared with other holographic materials such as dichromated gelatin and silver halide emulsions, photopolymers have the great advantage of recording and reading holograms in real time and the spectral sensitivity could be easily shifted to the type of recording laser used by simply changing the sensitizing dye. Also these materials possess characteristics such as good light sensitivity, real time image development, large dynamic range, good optical properties, format flexibility, and low cost. This thesis describes the attempts made to fabricate highly economic photopolymer films for various holographic applications. In the present work, Poly (vinyl alcohol) (PVA) and poly (vinyl chloride) (PVC) are selected as the host polymer matrices and methylene blue (MB) is used as the photosensitizing dye. The films were fabricated using gravity settling method. No chemical treatment or pre/post exposures were applied to the films. As the outcome of the work, photopolymer films with more than 70% efficiency, a permanent recording material which required no fixing process, a reusable recording material etc. were fabricated.

Methylene Blue Doped Polymers:Efficient Media for Optical Recording

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8 and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Complex methylene-blue-sensitized polyvinyl chloride: a polymer matrix for hologram recording

A new polymer matrix sensitized with methylene blue for use as an optical recording material is described here. The characterization is done to determine the optimal recording conditions. These films need no chemical development and are found to be stable for several months. The matrix has excellent shelf life and needs an exposure only as short as 20 s. Direct imaging was done on this material.

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Light amplification in dye doped polymer films

We report unusual spectral narrowing and laser emission from polymer thin films doped with Coumarin 540 dye. The laser emission from the polymer films is found to be highly dependent upon the excitation length of the medium. Even a short length of 1.75 mm of the dye doped film gave rise to laser emission with FWHM of 0.3 nm for a pump intensity of 825 kW cm−2. The partial reflections from the broad lateral surfaces of the free standing films provided the optical feedback for the laser emission. Occurrence of well-resolved equally spaced resonant modes confirmed the effect of a Fabry–Perot-like optical cavity between the film surfaces

Loss characterization in rhodamine 6G doped polymer film waveguide by side illumination fluorescence

We report the position dependent tuning of fluorescence emission from rhodamine 6G doped polymethylmethacrylate film waveguide using a side illumination technique. The transmitted fluorescence as a function of the distance from the point of illumination is measured by translating the waveguide horizontally across a monochromatic light source. This technique has been utilized to characterize the optical loss in dye doped waveguides. We observe that the optical loss coefficients for shorter and longer distances of propagation through the dye doped waveguide are different. At longer distance of propagation a decrease in optical loss coefficient is observed

Studies on Photosensitive polymers for Optical Recording

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

Realization of Optical Logic Gates Using the Thermal Lens Effect

A sensitive method based on the principle of photothermal phenomena to realize optical logic gates is presented. A dual beam thermal lens method using low power cw lasers in a dye-doped polymer can be very effectively used as an alternate technique to perform the logical function such as NAND, AND and OR.