A set of polyaniline- and poly(3,4-ethylene dioxythiophene)-based materials were studied as hole injection layers in polymer light emitting devices. The choice of polymeric counterion/dopant poly(styrenesulfonic acid), and poly(acrylamido-2-methyl-1-propanesulfonic acid), and poly(acrylamide) blended with polyaniline/poly(acrylamido-2-methyl-1-propanesulfonic acid) was found to influence both work function and film morphology, which in turn affects device performance. The work functions of the polymer films spanned the range of over 1 eV and the surface region of the films were found to be low in conducting polymer content compared to the bulk. This was particularly the case of the polyaniline/poly(acrylamido-2-methyl-1-propanesulfonic acid) blended with poly(acrylamide) which showed device efficiency equal to that of the poly(3,4-ethylene dioxythiophene)–poly(styrenesulfonic acid) reference. The turn on voltage, however, was significantly larger, likely due to the insulating poly(acrylamide)-rich surface region of the polyaniline/poly(acrylamido-2-methyl-1-propanesulfonic acid)/poly(acrylamide) film. The polymer blend of polyaniline/poly(styrenesulfonic acid) yielded the highest work function (5.5 ± 0.1 eV).

We present a study of poly(3,4-ethylene dioxythiophene), PEDOT, and polyaniline, where poly(perfluoroethylenesulfonic acid), PFESA has been used as counter ion and dopant respectively. The study was done in order to establish how the material petfonns as hole injecting layers in polymer light emitting devices. A total of 19 different PEDOT-PFESA samples and three different PAni-PFESA systems were studied, each with a different acidity, ranging between pH 1.6 to pH 7.7. The highest work function obtained was 6.0 eV and work function and acidity correlate such that significantly higher work functions are obtained for higher acidities. Photoelectron spectroscopy and Atomic Force Microscopy data suggest that the resulting fihns have grain structured morphology where the PAni-PFESA and PEDOT-PFESA systems form inverse micelles, i.e. PEDOT or PAni together with counter ions as an inner core surrounded by mainly the PFESA backbone.

The electronic structure of tetracyanoethylene (TCNE) has been studied both in its pristine state and upon stepwise rubidium intercalation, by UV and x-ray photoelectron spectroscopy as well as with theoretical calculations. The intercalated system may serve as a model for TCNE-based organometallic magnets, of which the electronic structure remains largely unknown. Rubidium is found to n-dope the TCNE molecules forming Rb⁺TCNE^- with almost complete charge transfer. Calculations show a spin splitting of the former highest occupied molecular orbital level upon Rb doping. We see no evidence for the formation of doubly charged TCNE molecules. A gap opens up at the Fermi energy for Rb⁺TCNE^- due to on-site Coulomb interactions. We estimate the on-site Coulomb interaction of amorphous TCNE doped with Rb to be ∼2 eV.