The photo-oxidation behavior of three different polymersnamely, poly(3-hexylthiophene) (P3HT), poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (C-PCPDTBT), and poly[2,6-(4,4-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-alt-4,7-(2,1,3-benzothiadiazole)] (Si-PCPDTBT)is investigated in neat polymer films and in blends with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) for different polymer:PCBM ratios. PCBM is shown to have both stabilizing and destabilizing effects, the extent of which is dependent on the type of polymer with which it is blended. Screening of the polymer from incident light by PCBM turns out to play an only minor role in the stabilization of P3HT. Quenching of the polymer excited states is also not a significant stabilization mechanism, as demonstrated by the comparison of the reduction of photo-oxidation rates to the extent of photoluminescence quenching by PCBM and 2,7-dinitrofluorenone (DNF). Photoinduced absorption spectroscopy reveals that the enhanced degradation of C-PCPDTBT in blend films with PCBM correlates with the population of the polymer triplet state via the polymer:PCBM charge-transfer state.

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.