The absorption spectrum of polythiophene and its derivative poly͑3-hexylthiophene͒ ͑P3HT͒ is usually described in terms of an intrachain exciton coupled to a single phonon mode. We show that this model is too simplistic for highly ordered, regioregular P3HT and that, analogous to the case of charged polarons in this material, interchain interactions must be taken into account to correctly describe the absorption spectrum. We show that the lowest energy feature in the-* region of the absorption spectrum is associated with an interchain absorption, the intensity of which is correlated with the degree of order in the polymer. Correspondingly, we show that the emission from P3HT also exhibits contributions from both interchain and intrachain states, in a manner similar to that recently shown for poly͑phenylenevinylene͒. Having reinterpreted the physical origin of the features in the absorption and emission spectra of P3HT, we then model these spectra and show how they evolve as the degree of order in the polymer is changed by varying several physical parameters including temperature and regioregularity of the polymer.

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The influence of device structure on the open-circuit voltage of polyfluorene-based photovoltaic devices has been investigated. Bilayers of hole- and electron-accepting polyfluorenes have been fabricated using an aqueous “float-off” lamination technique and subsequently incorporated into organic photovoltaic devices with a range of cathodes and anodes. A scaling of the open-circuit voltage with electrode work function difference has been observed with an additional intensity- dependent contribution from the active layer within the device. This additional contribution is attributed to photoinduced generation of carriers, whereby accumulation of charge at the polymer–polymer heterojunction results in a dipole across the interface and gives rise to a diffusion current that must be counterbalanced by a drift current at open circuit.

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Structural information about the degree of chain alignment in thin polymer films can be obtained by ellipsometry. A combination of reflection and transmission ellipsometry has been employed to determine the ordinary and extraordinary optical constants in conjugated polymer films in both the absorbing and transparent regions. Optical constants obtained by this technique will allow accurate modeling of the optical structure of polymer light‐emitting diodes (LEDs) and photodiodes.