Chapter 1 introduces the theme and motivation for the present work and Chapter 2 illustrates the materials and methods employed in a more comprehensive manner. Chapter 3 describes the stabilization of the -AgI thin films using the iodination of different surface modified Ag precursors, i.e. Mesoporous Ag foils, Ag-Cu Films and Ag-Sb Films, their structural and optical characterization. In Chapter 4, a simple-minded formulation of the silver-iodine reaction has been attempted to explain phenomenologically the ambient iodination procedure. Chapter 5 analyzes the complex electrical behavior of the Ag-rich Ag1-xCuxI (0 x 0.25) solid solutions in terms of obtaining a better understanding for the microscopic origin of superionic conductivity in these metal halide systems. Chapter 6 presents the dilatometry and HT-XRD measurements on polycrystalline AgI, CuI and their cation enriched solid solutions, providing a further insight into the structure-property correlations as well as the visualization of a near zero thermal expansion material in these disordered systems. Finally, a brief summary of all the above work is presented along with a few suggestions for the future work.