The conductivity of chemically and electrochemically de-doped poly(3,4-ethylenedioxythiophene) (PEDOT) has been investigated in situ. We observe a decrease in the conductivity by 4-5 orders of magnitude. The change of conductivity is correlated to the change of electronic structure. We obtain the dielectric function of the polymer by spectroscopic ellipsometry and note that anisotropy is observed in both doped and neutral states. © 2002 Elsevier Science B.V. All rights reserved.

Anisotropic optical constants spectrum of spin-coated thin films of poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate) (PEDOT-PSS) from 200 to 1700 nm were determined using variable-angle spectroscopic ellipsometry and polarized intensity transmission data together with absorption spectroscopy. PEDOT-PSS was found to be very anisotropic, uniaxial with the optic axis parallel to the surface normal. The result is in good agreement with results obtained of chemically polymerized PEDOT layers doped with toluenesulfonate. By adding sorbitol to the PEDOT-PSS dispersion before spin-coating, layers with a higher conductivity were obtained. A detailed study was made of the optical response of these layers in comparison to the PEDOT-PSS prepared from dispersions without sorbitol. The optical anisotropy is important to consider when using PEDOT-PSS in optoelectronic devices, such as polymer light-emitting diodes and photovoltaic devices. © 2002 Elsevier Science B.V. All rights reserved.

We study the emission zone in a single-layer polymer light-emitting diode. The emission zone is found by studying the angular distribution of the electroluminescence. The emission is modeled by accounting for optical interference. We account for birefringence of the anode layer in our model. The active polymer was, however, found to be isotropic. The anode consists of a single-layer of the conducting polymer complex poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (PEDOT-PSS), with enhanced conductivity. As a cathode we use plain aluminum. By using only PEDOT-PSS we avoid having a thin metal layer or indium-tin-oxide as the anode in the path of the escaping light. The active material is a substituted polythiophene with excellent film forming properties. A comparison between the experimental and calculated angular distribution of light emission from a single-layered polymer light-emitting diode was shown to be in good agreement for the spectral region studied. By assuming a distribution of the emission zone, we deduce the position as well as the width of the zone. (C) 2001 American Institute of Physics.

Ultraviolet spectroscopy (UPS) and x-ray photoelectron spectroscopy (XPS) were used to study the valence electronic structures of pristine and sodium doped poly (p-pyridine) (PPY). The UPS spectra were analyzed by studying the density-of-valence-states (DOVS) derived from quantum chemical calculations. The electronic band structure of the PPY chains was also theoretically investigated using the valence effective Hamiltonian (VEH) method. The theoretical approach was found to be more accurate in describing the electronic structure of PPY.

We present an analysis of the internal monochromatic quantum efficiency of photovoltaic devices based on polymer and polymer/fullerene thin films. A quantum efficiency of exciton-to-charge generation is defined as the external monochromatic quantum efficiency normalized to the absorption in the active materials of the device. An upper limit of the efficiency can be determined, and results show that much of the light is absorbed in photoactive layers of the device, whereas only a fraction of the generated excitons is converted to charge carriers and can be collected as photocurrent. © 2001 American Institute of Physics.

X-ray diffraction on samples in the form of a deposited thin layer, a crushed powder and a flake were used to deduce models for the crystalline structure of polypyridine (-(C5H3N)n-), a conjugated polymer of great interest for applications. A monoclinic unit cell with lattice parameters a = 7.47 Å, b = 5.83 Å, c = 4.25 Å, ? = 108.7° containing two chains running along the c-axis and with the molecular plane normal to the a-axis gives a good fit with the observations. The interchain packing distance is about 3.6 Å, i.e. in the same range as intermolecular distances found in conductive charge transfer salts. The deposited layer is highly anisotropic, with the a-c-plane parallel to the substrate. © 2001 Elsevier Science B.V. All rights reserved.

The equivalence principle is utilized for generation of both incident plane waves and for near- to far-zone transformation in the finite-difference time-domain (FDTD) method. Small errors will appear due to numerical dispersion when a plane wave is generated by Huygens' sources using an analytical expression fur the incident field. These errors can be derived from the numerical dispersion relation in the frequency domain. By using a second-order approximation of the numerical wavenumber it is shown that a simple approximative time-domain compensation procedure for the dispersion can be derived. This has been implemented in a Huygens' source routine and in a time-domain near- to far-zone transformation routine. It is shown that this compensation significantly reduces the errors produced when calculating far-zone scattered fields of low amplitude. It is also shown that it is sufficient to compensate either the Huygens' sources or the time-domain near- to Far-zone transformation with respect to dispersion. For validation, plane wave propagation through empty space and scattering of a dipole have been studied.

We report studies of a thin film multilayer stack including a highly emissive substituted polythiophene, poly[3-(2,5-dioctylphenyl)thiophene]. Analysis of the photoluminescence spectra revealed an inhomogeneous polymer film. X-ray diffraction studies attribute the existence of an inhomogeneous film as originating from crystallization of the polymer. We used the interference effect of light to detect the region of crystallization in the film. Photoluminescence and absorption were redshifted upon crystallization and displayed an enhanced vibronic structure. Comparison between calculated and measured photoluminescence shows that the crystallization starts from the top of the film and not from the supporting substrate. (C) 2000 American Institute of Physics. [S0021- 8979(00)08112-3].

The structural anisotropy of various poly(alkylthiophene) films have been studied by X-ray diffraction, using both conventional methods and synchrotron radiation at grazing incidence. Solution-cast films orient with the side chains preferably normal to the film surface, whereas spin-cast films of nonstereoregular material orient with both the main and the side chains in the film plane. For thick (10-50 µm) solution-cast films, the degree of orientation depends strongly on the solvent used for casting, and on the stereoregularity of the polymer, films of stereoregular materials being more oriented than those of nonregular materials. The most oriented nonregular films are those cast from mixtures of chloroform and tetrahydrofuran. Thin (50-500 nm) solution-cast films are more oriented than the thicker ones, and the effects of different stereoregularity or different casting solvents are small. For spin-cast films, the degree of orientation is independent of substrate and solvent. Spin-cast films of stereoregular material have two different phases: One with the side chains normal to the substrate, and another where they are parallel to the substrate. The diffraction peaks of spin-cast poly(octylthiophene) narrow considerably upon heating.