The molecule-based magnet V (TCNE)x, with TCNE=tetracyanoethylene, x˜2, shows an exceptionally high magnetic ordering temperature of about 400 K. With the aim to shed light on the origins of the robust magnetic ordering interactions, we have characterized the chemical bonding in V (TCNE)x thin films, prepared by an in situ chemical vapor deposition method, using photoelectron spectroscopy, x-ray absorption spectroscopy (XAS), and x-ray magnetic circular dichroism (XMCD). The XAS and XMCD results were interpreted by ligand field multiplet and charge transfer multiplet calculations, which show that the V-NC bonds are characterized by a large crystal field parameter 10Dq=2.3 eV and strong ligand to metal charge transfer effects, resulting in a hybrid V (3d) -CN ground state given by 60% 3 d3 and 40% 3 d4 L, where L is a hole on the cyano ligands. © 2007 The American Physical Society.

The fundamentals of the energy level alignment at anode and cathode electrodes in organic electronics are described. We focus on two different models that treat weakly interacting organic/metal (and organic/organic) interfaces: the induced density of interfacial states model and the so-called integer charge transfer model. The two models are compared and evaluated, mainly using photoelectron spectroscopy data of the energy level alignment of conjugated polymers and molecules at various organic/metal and organic/organic interfaces. We show that two different alignment regimes are generally observed: (i) vacuum level alignment, which corresponds to the lack of vacuum level offsets (Schottky-Mott limit) and hence the lack of charge transfer across the interface, and (ii) Fermi level pinning where the resulting work function of an organic/metal and organic/organic bilayer is independent of the substrate work function and an interface dipole is formed due to charge transfer across the interface. We argue that the experimental results are best described by the integer charge transfer model which predicts the vacuum level alignment when the substrate work function is above the positive charge transfer level and below the negative charge transfer level of the conjugated material. The model further predicts Fermi level pinning to the positive (negative) charge transfer level when the substrate work function is below (above) the positive (negative) charge transfer level. The nature of the integer charge transfer levels depend on the materials system: for conjugated large molecules and polymers, the integer charge transfer states are polarons or bipolarons, for small molecules' highest occupied and lowest unoccupied molecular orbitals and for crystalline systems, the relevant levels are the valence and conduction band edges. Finally, limits and further improvements to the integer charge transfer model are discussed as well as the impact on device design. © IOP Publishing Ltd.

Photoelectron spectroscopy was employed to examine the energetics, and therefore charge injection barriers, at top and bottom contact configurations of gold and conjugated polymers, i.e., polymer spin coated on gold and vapor-deposited gold on polymer interfaces. Very similar results are obtained for both ex situ (contaminated) and in situ (clean) prepared interfaces: a 0.7-0.8 eV decrease in the vacuum energy levels is consistently observed as compared to bare polycrystalline gold. These observations are explained by changes of the metal work function upon contacting either polymers or contaminants, associated with the reduction of the electron density tail that extends outside the metal surface. © 2006 American Institute of Physics.

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.

We describe a simple method to increase the work function of poly(3,4-ethylenedioxy-thiophene)-poly(perfluoroethylene sulfonic acid), PEDOT-PFESA, and poly(3,4-ethylenedioxy-thiophene)-poly(styrene sulfonic acid), PEDOT-PSS, by short exposure to ultraviolet light and ozone. The creation of carbonyl groups in the surface region forms 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 eV. The increase in work function has also proven to be time dependent with the largest increasing rate occurring for short exposure times. Upon ozone treatment, both PEDOT and PSS are oxidized whereas PFESA seems to be unaffected.

Thin films of V(TCNE)x were deposited in ultrahigh vacuum using a 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 oxygen-free films. X-ray magnetic circular dichroism measurements recorded at the V L2,3 edge confirmed room temperature magnetic ordering. A combination of conventional photoelectron spectroscopy (PES) and resonant photoemission (RPE) measured at the V L3 edge shows that the highest occupied electronic state is V(3d) derived. The rearrangements of the TCNE- related valence electronic states observed in PES and the evidence of V(3d) and TCNE- p(p*) orbital overlap contained in RPE spectra, indicate that strong, covalent type bonding occurs between the vanadium and the TCNE molecules. © 2006 The American Physical Society.

The electronic structure of materials for use in organic electronics is studied in this thesis. The first part includes applied research in the form of studies of polymers for use in polymer light emitting devices. The second part is more directed toward organic based spintronics and contains research regarding a room temperature organic ferrimagnetic material. Common for the studies, apart from that all regard organic material, are the use of electron spectroscopy techniques. The studies give new spectroscopic evidence of how the energy level alignment occurs between electrical conductors and spin coated semiconducting polymers, i.e. alignment at the anode side of polymer light emitting devices. The studies prove theoretical predictions regarding spontaneous charge injection forming positive polaronic species in the semiconducting polymer, pinned to the Fermi level of the substrate. The first part also includes studies of novel conducting polymers, based on PEDOT and polyaniline, with work functions spanning from 4.2 eV to 6.4 eV. In the case of organic magnets, our design and construction of the purpose built vacuum deposition system allowed for the first time oxygen free films of the extremely reactive organic ferrimagnet, vanadium tetracyanoethylene (V(TCNE)x), to be studied by means of several different electron spectroscopies, proving or disproving several previous results and assumptions.

Orbital-specific femtosecond charge transfer dynamics between Fe(II)-tetraphenylporphyrin molecules and semimetallic molybdenum disulfide substrates is investigated using core-level resonant photoemission spectroscopy. The electronic coupling to the substrate and the efficiency of charge transport across the interface is found to be different for the individual molecular electronic subsystems. In particular, electrons excited at the phenyl substituents are transferred within 3–6 fs, while hopping from the porphyrin ring is slower than 30 fs.

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).