Photogeneration and transport of charge carriers in hybrid materials of conjugated polymers and dye-sensitized TiO2

Steady state photoconductivity and current-voltage (I-V) experiments are performed on solid films of organic/inorganic composites of dye-sensitized TiO2 in combination with poly(N-vinylcarbazole) (PVK), a ladder-type PPP and a soluble PPV derivative. The I-V characteristics of the composites in the dark are explained by the formation of percolation networks of nanoparticles between the electrodes. Photoaction spectra of the devices prove that the photogeneration of charge carriers is significantly enhanced and spectrally broadened only if electron transfer from the polymer to the dye is possible. Increasing the concentration of the nanoparticles in the hybrid materials changes the spectral shape of the photoresponse. For high TiO2 contents signatures due to the absorption of the Ruthenium dye can be observed. The different electronic properties of anatase/brookite TiO2 and rutile TiO2 have only minor effects on the generation of charge carriers and on the shape of the photoaction spectra. Indeed, photocurrents are more related to the Brunauer-Emmett-Teller surface area of the nanoparticles and thus, to the amount of dye adsorbed. Charge collection efficiencies exceeding 100%, observed for both bias directions, can be explained by photoconductivity gain. It is proposed that recombination is reduced by transport of the oppositely charged carriers in two different phases. (C) 1999 American Institute of Physics. [S0021-8979(99)02024-1].