We report measurements made on the photovoltaic effect in devices fabricated with thin films of α-sexithienyl (αT6) as the active layer. aT6 was sublimed onto glass/ITO substrates (as the positive contact), and the substrate temperature was varied between room temperature and 156°C during sublimation to control the film morphology. As the substrate temperature increases, the average size of the αT6 grains increases, from ˜200nm at 22° C to ˜1500nm at 150°C, and order within the grains increases. Aluminium metal was evaporated onto the αT6 as the top (negative) contact.

The dark current-voltage (I-V) curve is strongly rectifying, whereas under illumination it becomes almost symmetrical about ˜0.7V on the voltage axis, which represents the maximum open-circuit voltage. This behaviour indicates that the efficiency of charge separation is strongly bias dependent, and that charges are separated by the bulk field rather than at, for example, a Schottky barrier. The spectral response of the photocurrent is independent of the film morphology, which is surprising since the environment in which excitons recombine radiatively in αT6 is known to depend on the morphology of the film. The spectral response is consistent with previous measurements on photoconductivity, indicating that the efficiency of charge separation increases with increasing photon energy. There is also a significant photocurrent at energies well below the absorption edge of αT6, suggesting an exponential distribution of defect states extending at least 0.6eV into the optical gap, which may be a distribution of X-traps below the absorption edge. As the substrate temperature during growth increases from 28C to 150C the efficiency of charge separation decreases by an order of magnitude, suggesting that exciton dissocation is assisted by traps or defects which are present in smaller numbers in the more ordered films.