The degradation and failure mechanisms of a stable photovoltaic device comprising a bilayer heterojunction formed between poly(3-carboxythiophene-2,5-diyl-co-thiophene-2,5-diyl) (P3CT) and Buckminsterfullerene (C-60) sandwiched between indium tin oxide (ITO) and aluminium (Al) electrodes were elucidated by the time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis in conjunction with isotopic labelling using O-18(2) after a total testing time of 13 000 h. This experiment allowed us to understand the chemistry that takes place in three dimensions during degradation and failure of the device under accelerated testing conditions. The cell was subjected to continuous illumination with an incident light intensity of 1000 W m(-2) (AM1.5) at 72 +/- 2 degrees C under a vacuum of