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.

We describe a simple method to increase the work function of PEDOT-PFESA and PEDOT-PSS by short exposure to UV and ozone in a "UVO-Cleaner®". The creation of carbonyl gmups in the surface region fotms a dipole layer shifting the vacuum level with a followed increase in work function. It has been shown that the work function of PEDOT-PFESA can be increased by as much as -0.4 eV to the absolute value of 6.3 eV and by at least -0.2 eV for PEDOT-PSS to the absolute value of 5.4 e V. The increase in work function has also proven to be time dependent with the largest increasing rate occuning for short exposure times. Upon ozone treatment, both PEDOT and PSS are oxidized whereas PFESA seems to be unaffected.

Photoelectron spectroscopy has been used to map out energy level alignment of conjugated polymers at various organic-organic and hybrid interfaces. Specifically, we have investigated the hole-injection interface between the substrate and light-emitting polymer. Two different alignment regimes have been observed: (i) Vacuum-level alignment, which corresponds to the lack of vacuum-level offsets (Schottky–Mott limit) and (ii) Fermi-level pinning, where the substrate Fermi level and the positive polaronic level of the polymer align. The observation is rationalized in terms of spontaneous charge transfer whenever the substrate Fermi level exceeds the positive polaron/bipolaron formation energy per particle. The charge transfer leads to the formation of an interfacial dipole, as large as 2.1 eV.

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.

We have prepared and characterized thin films of V(TCNE)_x in ultra-high vacuum using a novel film growth technique based on in-situ chemical vapor deposition of tetracyanoethylene, TCNE, and bis-benzene vanadium, V(C₆H₆)₂. The in-situ preparation method enabled, for the first time, experimental analysis of the electronic structure. X-ray magnetic circular dichroism (XMCD) measurements recorded at the V L_2,3-edge confirmed room temperature magnetic ordering. A combination of conventional photoelectron spectroscopy (PES) and resonant photoemission (RPE) measured at the x-ray absorption edges (V L₃-edge, C K-edge, N K-edge) shows that the highest occupied electronic state is V(3d)-derived. Nearly complete quenching of the V(3d) orbital angular momentum is observed from the low value of the integrated XMCD signal, indicating a strong ligand field. The rearrangements of the TCNE" related valance electronic states observed in PED and near edge x-ray absorption fine structure (NEXAFS) spectra, in combination with the evidence of V(3d) and TCNE" π (π^*) orbital overlap contained in RPE spectra, also point to strong, covalent type bonding.