Mechanism of the Alcohol-Soluble Ionic Organic Interlayer in Organic Solar Cells

In this article combining density functional theory (DFT) calculations and corresponding experimental measurements, the adsorption behaviors and working mechanism of the alcohol-soluble ionic organic interlayer on different electrode substrates were studied. The results suggest that, when the ionic organic bipyridine salt interlayer (FPyBr) is adsorbed on the Ag surface, Br^- will break away from molecule chains and form new chemical bonds with the Ag substrate, as confirmed by both the X-ray photoelectron spectroscopy (XPS) study and DFT study for the first time. Charges are further found to transfer to the Ag substrate from the new interlayer molecular structure without Br^-, resulting in adsorption dipoles directed from Ag to the interlayer. Moreover, the direction of the intrinsic dipole of the molecule itself on the Ag substrate is also verified, which is the same as that of the adsorption dipole. Subsequently, the superposition of the two dipoles results in a large reduction of the Ag substrate work function. In addition, the dipole formation mechanism of the interlayer on the ITO surface was also studied. The change in the work function of the ITO substrate by this interlayer is found to be smaller than that of Ag as confirmed by both a DFT study and scanning Kelvin probe microscopy (SKPM) results, which is mainly due to the reversed direction of the molecular intrinsic dipole with respect to the interfacial dipole. The worst device performance of organic solar cells based on the ITO-FPyBr substrate is considered to be one of the consequences of the feature. The findings here are of great importance for the study of the mechanism of the ionic organic interlayer in organic electronic devices, providing insightful understandings on how to further improve the material and device performance.