Contactless Determination of the Photoconductivity Action Spectrum, Exciton Diffusion Length, and Charge Separation Efficiency in Polythiophene-Sensitized TiO2 Bilayers

The flash-photolysis time-resolved microwave conductivity technique (FP-TRMC) has been used to study photoinduced charge separation in bilayers consisting of a smooth, transparent, 80 nm thick layer of anatase TiO2 onto which poly(3-hexylthiophene) (P3HT) sensitizer layers have been spin-coated. Interfacial charge separation, resulting from excitation of the polymer in the visible, is found to persist well into the millisecond time domain. Photoconductivity action spectra have been measured between 420 and 700 nm for P3HT layer thicknesses, L, from ∼2 to 200 nm. Using this electrodeless technique, the bilayers could be irradiated from either the polymer (“front”) or semiconductor (“back”) side. On front-side irradiation at 540 nm (close to the absorption maximum of the polymer), the efficiency of charge separation per incident photon (IPCSE) initially increased to a maximum value of 0.8% for L ≈ 10 nm. For thicker layers the IPCSE gradually decreased, eventually to 0.1% for L ≈ 170 nm. On back-side irradi...