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The influence of oxygen and light on the energy level alignment of poly(3-hexylthiophene) thin films (∼100 nm) is investigated quantitatively using X-ray and ultraviolet photoelectron spectroscopy (XPS/UPS) in order to probe energetic shifts and the element distribution in the film. Upon simultaneous exposure to oxygen and light a reversible shift of the occupied states of about 0.3 eV is observed together with the presence of reversibly and irreversibly bound oxygen species. Whereas the reversibly bound species correlates with the energy shifts, the latter does not alter the electronic structure. The observations are discussed in terms of light-induced p-doping of the semiconducting material by oxygen which is completely reversible upon vacuum annealing of the polymer film above the glass transition temperature of 150 °C.

A study of how light‐induced degradation influences the fundamental photophysical processes in the active layer of poly(3‐hexylthiophene)/[6,6]‐phenyl C61‐butyric acid methyl ester (P3HT/PCBM) solar cells is presented. Non‐encapsulated samples are systematically aged by exposure to AM 1.5 illumination in the presence of dry air for different periods of time. The extent of degradation is quantified by the relative loss in the absorption maximum of the P3HT, which is varied in the range 0% to 20%. For degraded samples an increasing loss in the number of excitons within the P3HT domains is observed with longer ageing periods. This loss occurs rapidly, within the first 15 ps after photoexcitation. A more pronounced decrease in the population of polarons than excitons is observed, which also occurs on a timescale of a few picoseconds. These observations, complemented by a quantitative analysis of the polaron and exciton population dynamics, unravel two primary loss mechanisms for the performances of aged P3HT/PCBM solar cells. One is an initial ultrafast decrease in the polaron generation, apparently not related to the exciton diffusion to the polymer/fullerene interface; the second, less significant, is a loss in the exciton population within the photoexcited P3HT domains. The steady‐state photoinduced absorption spectra of degraded samples exhibits the appearance of a signal ascribed to triplet excitons, which is absent for non‐degraded samples. This latter observation is interpreted considering the formation of degraded sites where intersystem crossing and triplet exciton formation is more effective. The photovoltaic characteristics of same blends are also studied and discussed by comparing the decrease in the overall power conversion efficiency of solar cells.