Photophysical and Electrochemical Investigations on Photoconducting Poly(6-tert-butyl-3,4-dihydro-2H- 1,3-benzoxazine)

Poly(6-tert-butyl-3,4-dihydro-2H-1,3-benzoxazine) was synthesized by thermally activated cationic ring opening polymerization. The structure of the polymer was confirmed by spectral and thermal studies. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated using cyclic voltammetry and optical absorption. Modulated photocurrent measurement technique was employed to study the spectral and field dependence of photocurrent. Photocurrent of the order of 1.5 micro A/m2 was obtained for polymer at a biasing electric field of 40 V/mico m.

Development of Macrocyclics based Electrochemical Sensors

Electroanalytical techniques represent a class of powerful and versatile analytical method which is based on the electrical properties of a solution of the analyte when it is made part of an electrochemical cell. They offer high sensitivity, accuracy, precision and a large linear dynamic range. The cost of instrumentation is relatively low compared to other instrumental methods of analysis. Many solid state electrochemical sensors have been commercialised nowadays. Potentiometry is a very simple electroanalytical technique with extraordinary analytical capabilities. Since valinomycin was introduced as an ionophore for K+, Ion Selective Electrodes have become one of the best studied and understood analytical devices. It can be used for the determination of substances ranging from simple inorganic ions to complex organic molecules. It is a very attractive option owing to the wide range of applications and ease of the use of the instruments employed. They also possess the advantages of short response time, high selectivity and very low detection limits. Moreover, analysis by these electrodes is non-destructive and adaptable to small sample volumes. It has become a standard technique for medical researchers, biologists, geologists and environmental specialists. This thesis presents the synthesis and characterisation of five ionophores. Based on these ionophores, nine potentiometric sensors are fabricated for the determination of ions such as Pb2+, Mn2+, Ni2+, Cu2+ and Sal- ion (Salicylate ion). The electrochemical characterisation and analytical application studies of the developed sensors are also described. The thesis is divided into eight chapters

Structural, electrical and electrochemical characterization of high frequency magnetron sputtered spinel oxide cathode films for lithium ion battery applications

The main challenges in the deposition of cathode materials in thin film form are the reproduction of stoichiometry close to the bulk material and attaining higher rates of deposition and excellent crystallinity at comparatively lower annealing temperatures. There are several methods available to develop stoichiometric thin film cathode materials including pulsed laser deposition; plasma enhanced chemical vapor deposition, electron beam evaporation, electrostatic spray deposition and RF magnetron sputtering. Among them the most versatile method is the sputtering technique, owing to its suitability for micro-fabricating the thin film batteries directly on chips in any shape or size, and on flexible substrates, with good capacity and cycle life. The main drawback of the conventional sputtering technique using RF frequency of 13.56MHz is its lower rate of deposition, compared to other deposition techniques A typical cathode layer for a thin film battery requires a thickness around one micron. To deposit such thick layers using convention RF sputtering, longer time of deposition is required, since the deposition rate is very low, which is typically 10-20 Å/min. This makes the conventional RF sputtering technique a less viable option for mass production in an economical way. There exists a host of theoretical and experimental evidences and results that higher excitation frequency can be efficiently used to deposit good quality films at higher deposition rates with glow discharge plasma. The effect of frequencies higher than the conventional one (13.56MHz) on the RF magnetron sputtering process has not been subjected to detailed investigations. Attempts have been made in the present work, to sputter deposit spinel oxide cathode films, using high frequency RF excitation source. Most importantly, the major challenge faced by the thin film battery based on the LiMn2O4 cathode material is the poor capacity retention during charge discharge cycling. The major causes for the capacity fading reported in LiMn2O4cathode materials are due to, Jahn-Teller distortion, Mn2+ dissolution into the electrolyte and oxygen loss in cathode material during cycling. The work discussed in this thesis is an attempt on overcoming the above said challenges and developing a high capacity thin film cathode material.