This thesis presents the characterization of the optical and mechanical properties of silica nanoparticle films fabricated by ionic self-assembly, also known as layer-by-layer (LbL) deposition. Utilizing electrostatic attraction of oppositely-charged materials permits uniform and rapid growth of the constituents onto planar and curved surfaces. In this work, silica nanoparticles are adsorbed onto glass and polycarbonate substrates, as well as micron-scale glass fibers, with the purpose of improving the optical quality of the respective media. Several methods are presented to improve the adhesion and cohesion of silica nanoparticle films on glass substrates. In the first method, the substrate and nanoparticle surfaces are coated with materials containing sulfonate end groups. Next, a photo-reactive polycation known as diazo-resin (DAR) is used in ISAM deposition with the modified silica nanoparticles. Subsequent exposure to UV converts the ionic bonds between the DAR and sulfonate groups into covalent ones. The second method to improve the mechanical strength is to heat the ISAM silica nanoparticle film at a high enough temperature (500 °C) to remove the polymer and partially fuse the nanoparticles. This technique is known as calcination and is shown to significantly improve the mechanical robustness of the film without compromising the optical properties. The final method involves the deposition of precursor and capping polymer layers around bulk silica nanoparticle films with both bilayer and quadlayer designs. The addition of these polymer layers improves the surface contact between adjacent nanoparticles but reduces the film porosity and consequently the optical transparency. Currently the calcination technique is the only one that significantly improves the film adhesion and cohesion, but suggestions are offered to potentially improve the performance of films made by the other two methods. An alternative way to functionalize polycarbonate substrates for silica nanoparticle ISAM deposition is also presented. The molecular structure of polycarbonate at the surface can be modified by exposing it to deep UV (λ = 185, 254 nm). By doing so, the surface becomes populated with carboxylate species, and thus permits ISAM deposition of poly(allylamine hydrochloride) (PAH) and silica nanoparticles. A variety of spectroscopic methods show that the molecular structure is changed by this procedure, and SEM shows that UV treatment improves the uniformity of ISAM films on polycarbonate. Finally, PAH/silica nanoparticle ISAM films are deposited onto glass fibers. The fibers are used for mechanical reinforcement of polymer composite optical media. The role of the nanoparticle film on the fibers is to reduce light scattering at the interfaces of materials with different thermo-optic coefficients, in other words, transmittance losses associated with changes in temperature. Fiber bundles coated with silica nanoparticles suffer from unacceptable levels of aggregation, and hence do not currently improve the transmittance over the temperature spectrum. Some evidence is presented, however, to suggest that the transparency can be improved if fiber aggregation during ISAM deposition can be avoided. / Ph. D.