Dipole Engineering for Conducting Polymers

Abstract

A method for the growth of a TiO2 adhesion layer on PEDOT:PSS (poly[3,4-ethylenedioxythiophene]: poly[styrenesulfonate]) and for further functionalization with self-assembled monolayers of phosphonates (SAMPs) was developed. The TiO2 adhesion layer was grown via chemical vapor deposition using a titanium(IV) t-butoxide precursor, and was characterized by goniometry and X-ray photoelectron spectroscopy. TiO2 grown on a model system, H-terminated silicon, indicated that the surface was t-butoxide terminated. Phenylphosphonic acids were synthesized with a variety of molecular dipoles and were used to change the work function of PEDOT:PSS through the formation of an aggregate surface dipole. Good correlation was found between the z component of the molecular dipole and the change in work function, indicating that the film was well-ordered and dense. The magnitude of the changes in work function and goniometry measurements were similar to measurements on ITO, a substrate on which phosphonates form well-ordered monolayers. As-grown PEDOT:PSS/TiO2 electrodes showed a lower work function compared to PEDOT:PSS, which is attributed to residual t-butoxide groups on the TiO2 surface. UPS measurements revealed that reductions in work function in the modified electrodes lowered the difference in energy between the Fermi energy (EF) of the conducting polymer and the LUMO of PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). A reduction of this energy difference should translate into increased electron injection in electron-only diodes; however, devices with modified electrodes showed decreased current densities. UPS/IPES measurements show that TiO2 grown using this method has a much larger band gap than bulk or nanocrystalline TiO2, which is likely responsible for this decrease in device currents. At high bias, device currents increase dramatically, and the effects of the phosphonates or t-butoxide terminated TiO2 vanish. This is attributed to a reduction of the TiO2 to conducting TiO2-x and the phosphonates to non-binding phosphinates, which is facilitated by the acidic protons in PEDOT:PSS.