Surface photovoltage (SPV) spectra are reported for separate films of (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) and for regioregular and regiorandom poly(3-hexylthiophene) (P3HT):PCBM bulk heterojunctions, as a function of wavelength, film thickness, thermal annealing, and substrate. In PCBM films, two photovoltage features are observed at 1.1–1.4 eV (F1) and 1.4–2.3 eV (F2), which are assigned to excitation of charge transfer states at the interface (F1) and in the bulk (F2) of the film. In BHJ films, five different photovoltage features are observed at 0.75–0.9 eV (F1), 0.9–1.3 eV (F2), 1.3–1.8 eV (F3), 1.8–2.0 eV (F4), and 2.0–2.4 eV (F5). This data can be analyzed on the basis of optical absorbance and fluorescence spectra of the films, and using SPV spectra for PCBM and P3HT only films, and for a BHJ film containing P3HT nanofibers for comparison. SPV features are assigned to states at the polymer–substrate interface (F1 and F2), the P3HT:PCBM charge transfer state (F3), the self-ionized (CT) state of P3HT (F4), and the band gap transition of P3HT (F5). This interpretation is also consistent with molecular orbital energy diagrams and electron microscopy-derived topological maps of the films. Photovoltage sign and substrate dependence can be understood with the depleted semiconductor model. Features F1–4 are caused by polarization of electrostatically bound charge pairs by the built-in electric field at the substrate–BHJ interface, whereas F5 is due to transport of free charge carriers through the film and through the substrate film interface. This work will promote the understanding of photochemical charge generation and transport in organic photovoltaic films.

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