Contact-free probing of interfacial charging and Debye-like charge screening in SiO$_2$/PDI8-CN$_2$ systems by optical second harmonic generation

TL;DR

This study uses optical second harmonic generation spectroscopy to non-invasively investigate interfacial charge distribution and screening effects in SiO₂/PDI8-CN₂ organic semiconductor systems, revealing localized charges and their physical origins.

Contribution

It introduces a model linking nonlinear susceptibility with Debye-Huckel screening to interpret interfacial charge phenomena in organic semiconductor/dielectric interfaces.

Findings

Identification of a charge-free region with broken inversion symmetry

Evidence of localized net charge at the SiO₂ interface

Physical origin linked to redox reactions involving water and PDI8-CN₂

Abstract

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.