Contact-free probing of interfacial charging and Debye-like charge screening in SiO₂/PDI8-CN₂ systems by optical second harmonic generation

Investigation of the interfacial electronic properties of N,N'-bis(n-octyl)-(1,7&1,6)-dicyanoperylene-3,4:9,10-bisdicarboximide (PDI8-CN2) organic semiconductor films grown on silicon dioxide is performed by polarization-resolved second harmonic generation optical spectroscopy, pointing out a spatial region where charge carriers distribution in the semiconductor lacks inversion symmetry. By developing a model for nonlinear susceptibility in the framework of Debye-Huckel screening theory, we show that the experimental findings can be interpreted as resulting from the presence of a net charge localized at the silicon dioxide, accompanied by a non-uniform charge distribution in the organic semiconductor. Photoluminescence analysis further reinforces this scenario. Reduction-oxidation reactions involving PDI8-CN2 and water molecules are invoked as physical origin of the localized charge. The work outlines a sensitive tool to probe the total charge localized at buried semiconductor/dielectric interfaces in organic thin-film transistors without resorting to invasive contact-based analyses.