Preparation and morphological and optical characterization of azo-polymer-based SiO2 sonogel hybrid composites

The well-established catalyst-free sonogel route was successfully implemented to fabricate highly pure, optically active, solid state polymeric azo- dye/SiO2-based hybrid composites. Bulk samples exhibit controllable geometrical shapes and monolithic structure with variable dopant concentrations. Since the implemented azo-dye chromophores exhibit a push–pull structure, hybrid film samples were spin-coated on ITO-covered glass substrates; molecular alignment was then performed via electrical poling in order to explore the quadratic nonlinear optical performance of this kind of composite. Comprehensive morphological, spectroscopic and optical characterization of the samples were performed with several experimental techniques: atomic force microscopy, x-ray diffraction and infrared, Raman, photoluminescent and ultraviolet–visible spectroscopies. The linear refractive indices of both bulk and thin film samples were measured according to the Brewster angle technique and a numerical analysis of the transmission spectral data, respectively. Regardless of the low glass transition temperatures of the studied polymers, some hybrid film samples were able to display stable nonlinear optical activity such as second harmonic generation. Results show that the chromophores were satisfactorily embedded into the highly pure SiO2 sonogel network without significant guest–host molecular interactions, thus preserving their optical properties and producing sol–gel hybrid glasses suitable for optical applications