Resonant inelastic soft-x-ray scattering spectra at the N1s and C1s edges of poly(pyridine-2,5-diyl)

Resonant inelastic scattering measurements of poly(pyridine-2,5-diyl) have been performed at the N1s and C1s edges using synchrotron radiation. For comparison, molecular orbital calculations of the spectra have been carried out with the repeat unit as a model molecule of the polymer chain. The resonant emission spectra show depletion of the p electron bands which is consistent with symmetry selection and momentum conservation rules. The depletion is most obvious in the resonant inelastic scattering spectra of carbon while the nitrogen spectra are dominated by lone pair n orbital emission of s symmetry and are less excitation energy dependent. By comparing the measurements to calculations an isomeric dependence of the resonant spectra is found giving preference to two of the four possible isomers in the polymer.Comment: 6 pages, 3 figures, http://www.sciencedirect.com/science/article/pii/S036820489800354

The electronic structure of poly(pyridine-2,5-diyl) investigated by soft x-ray absorption and emission spectroscopies

The electronic structure of the poly-pyridine conjugated polymer has been investigated by resonant and nonresonant inelastic X-ray scattering and X-ray absorption spectroscopies using synchrotron radiation. The measurements were made for both the carbon and nitrogen contents of the polymer. The analysis of the spectra has been carried out in comparison with molecular orbital calculations taking the repeat-unit cell as a model molecule of the polymer chain. The simulations indicate no significant differences in the absorption and in the non-resonant X-ray scattering spectra for the different isomeric geometries, while some isomeric dependence of the resonant spectra is predicted. The resonant emission spectra show depletion of the {\pi} electron bands in line with symmetry selection and momentum conservation rules. The effect is most vizual for the carbon spectra; the nitrogen spectra are dominated by lone pair n orbital emission of {\sigma} symmetry and are less frequency dependent.Comment: 11 pages, 7 figures, 1 table, http://www.sciencedirect.com/science/article/pii/S030101049800262

PRESSURE EFFECTS ON ELECTRICAL CONDUCTIVITIES IN INTERCALATED GRAPHITE AND DOPED POLYPYRROLE

Nous avons mesuré la résistivité électrique, jusqu'à 2.5 GPa et à la température ambiante, des graphites intercalés CnFeCl3, CnSbF5 et CnHNO3. L'augmentation de la résistance jusqu'à 2.5 GPa est sensiblement la même dans les trois cas. On a constaté une transition de phase dans chacun des deux derniers matériaux, les caractéristiques de ces transitions etant différentes. Nos résultats sur la variation de la résistance du polypyrrole sont en accord avec la théorie de "sauts à pas variable". II paraît que la densité d'états au niveau Fermi augmente avec la pression.We have measured the pressure dependence up to 2.5 GPa of the electrical resistance of the acceptor intercalated graphites CnFeCl3, CnSbF5, and CnHNO3. The slope of resistance versus pressure is approximately the same in all cases. Two different types of high pressure transitions are observed in CnSbF5 and CnHNO3. The results of electrical resistance measurements under pressure in polypyrrole are consistent with a simple extension of the variable-range-hopping model. We infer for this material that the density of states at the Fermi level increases with pressure

Modification of PEDOT-PSS by low-energy electrons

The stability of conjugated organic materials under electron transport is of great importance for the lifetime of devices such as polymer light-emitting diodes (PLEDs). Here, the modification of thin films of poly(3,4-ethylenedioxythiophene) oxidized with poly(4-styrenesulfonate) (known as PEDOT–PSS, often used in the fabrication of PLEDs) by low-energy electrons has been studied using X-ray photo-electron spectroscopy. Thin films of PSSH and molecular solid films of EDOT molecules also have been studied. We find that electrons with kinetic energies as low as 3 eV result in significant modification of the chemical structure of the materials. For thin films of PSSH, the electron bombardment leads to a strong loss of oxygen and a smaller loss of sulfur. In addition, a large amount of the sulfur atoms that remain in the films exhibits a different binding energy because of scissions of the bonds to oxygen atoms. For condensed molecular solid films of EDOT molecules, we find that the carbon atoms bonded to oxygen react and form additional bonds, as evidenced by a new component in the C(1s) peak at a higher binding energy. In the PEDOT–PSS blend, we find both effects. The importance of these observations for light-emitting diodes incorporating PEDOT–PSS films is discussed. This work demonstrates that the combination of in situ low-energy electron bombardment in combination with photo-electron spectroscopy is a powerful method to simulate and study certain processes, associated with low-energy electrons, occurring in organic based devices, which cannot be studied directly otherwise

Ultra-fast charge transfer in organic electronic materials and at hybrid interfaces studied using the core-hole clock technique

The focus of this brief review is the use of resonant photoemission in its “core-hole clock” expression for the study of two important problems relevant for the field of organic electronics: the dynamical charge transfer across hybrid organic–inorganic interfaces, and the intermolecular charge transfer in the bulk of organic thin films. Following an outline of the technique, a discussion of its applicability and a short overview of experimental results obtained thus far, two examples are used to illustrate particular results relevant for the understanding of the charge transport in organic electronic devices. First, for Fe(II)-tetraphenylporphyrin molecules on semi-metallic molybdenum disulfide substrates, the electronic coupling to the substrate and the efficiency of charge transport across the interface different for the individual molecular electronic subsystems is discussed. And second, a discotic liquid crystalline material forming columnar assemblies is used to illustrate ultra-fast intermolecular charge transfer on the order of a few femtoseconds indicating an electronic coupling between the phthalocyanine units stronger than expected from the macroscopic charge transport characteristics of the materia

Electronic structure of a novel alkylidene fluorene polymer in the pristine state

The electronic structure of a novel conjugated polymer, polyalkylidene fluorene has been studied using a combined experimental-theoretical approach. The densities of states in the valence band region of the new derivative, poly(9-(1'-decylundecylidene)fluorene), were measured by ultraviolet photoelectron spectroscopy and compared with electronic band-structure calculations performed in the valence effective Hamiltonian framework. The results are compared with those of similar studies on the reference polymer poly(9,9-dioctylfluorene). We report the experimentally determined ionization potential for this new material and discuss the role of substitution in altering the electronic properties of the polymer backbone