The interest in conjugated polymers has been two-fold. A rich variety of intriguing physical phenomena, combined with its immense technological implications in the area of molecular electronics, sensors etc. has inspired the researchers all over the globe. The work presented in this thesis is focussed on one of the most widely studied conjugated polymers, namely polyaniline (PANI), which is well known for its high conductivity and remarkable stability in the proton-doped form. The thesis is divided into two chapters and each chapter is further divided into several parts. In the first chapter, we take a look at some novel systems based on PANI that exhibit interesting electrical and optical properties. To begin with, we report the synthesis and characterization (Part I, Chapter 3) a new class of highly conducting polyaniline doped with electron deficient Lewis acids, namely the boron trihalides (BX3, X = F, Cl, and Br). We discuss the various attributes of this interesting class of materials that set it apart from the conventional proton-doped PANI systems. It is known that the conductivity in doped PANI is greatly influenced by the presence of structural disorder. Previous studies have associated the conductivity in doped PANI with the partial crystallinity that is achieved upon proton doping. At the same time, the amorphous regions that have a high degree of disorder were believed to suppress the metallic nature in these doped systems. In view of this "higher-crystallinity-higher-conductivity" picture, it is interesting to note that the BX3 doped PANI remain absolutely amorphous despite being more conducting than previously known samples. Through our investigation, we have been able to address some of the most important and long-standing questions pertaining to the nature of the charge carriers and the role of disorder in doped PANI. A detailed study of the transport properties in Part II, Chapter 3 helps us to understand the mechanism of charge transfer in these novel systems. With the help of our results, we establish that the present systems do not belong to the family of quasi one-dimensional conductors, in stark contrast to the conventional proton-doped samples. Instead, our systems are best described as granular metals, where the conduction mechanism is controlled by the size of the conducting grains and the nature of the grain boundaries. Through a comprehensive study of the magnetic properties based on d. c. magnetic susceptibility and EPR spectroscopy, we further establish that the intrinsic conductivity of these samples are much higher than the previously known systems. By studying the interaction of the mobile charge carriers and the localized spins in the systems, we have established that our samples are far less disordered, and therefore qualify as superior systems when compared to the more conventional proton-doped PANI. One of the serious disadvantages of the conventional protonated PANI lies in its thermal instability. On heating above 75 ±C in air, the polymer backbone undergoes an irreversible aerial oxidation that disrupts the extended conjugated structure. This is marked by a rapid drop in conductivity by a few orders of magnitude. BF3-doped PANI, which has the highest conductivity sample among the present series of samples, exhibits a remarkable thermal stability in air (Part III, Chapter 3). Upon heating, the conductivity initially increases and then reaches a saturation value. The polymer can be heated at temperatures as high as 225 ±C, without any signs of degradation. With the help of temperature dependent conductivity, XPS and FTIR spectroscopy we have tried to understand this unexpected phenomenon. In Part IV, Chapter 3, we report the synthesis and characterization of a novel class of functionalized PANI that exhibit an intense deep-blue photoluminescence. A de- tailed characterization based on absorption, photoluminescence, XPS, NMR and FTIR spectroscopy has been carried out to study the chemical state of this new class of light- emitting polymers. Further, we note that the synthetic procedure followed in this work can provide a very general route to the synthesis of diversely useful derivatives of PANI. In Chapter 4, we have investigated the microscopic origin of conductivity in doped PANI. Among the several factors that can influence the conductivity of doped polymers, one is the microstructural order. To understand this better, we carried out a detailed investigation, based on scanning tunneling microscopy (STM) and spectroscopy (STS) of undoped and doped PANI films (Part I, Chapter 4). We have shown for the ¯rst time that solution processed thin films of undoped PANI has an abundance of PANI anorods self organized over very large areas. Further, we observe that this ordered orphology is Preface vii very sensitive to the choice of dopants and the doping procedure. We have shown that the morphological order can greatly influence the electronic structure and therefore the properties of these systems. To understand the role of dopant-polymer interaction in controlling the conductivity of doped PANI, we carried out x-ray photoelectron spectroscopy (XPS) studies on a large number of partially and fully doped samples (Part II, Chapter 4). We find an interesting trend in the higher binding energy feature and the asymmetry of the N and C 1s spectra, which correlates directly with the respective conductivities of different samples. The analysis of these spectra brings out interesting facts about the chemical state and the electronic structure of these samples. In summary, we have reported new PANI based systems with improved electrical and interesting optical properties, and have studied various factors that influence the properties of these as well as some of conventional doped PANI systems.