The work focuses on the degradation of performance induced by both water and oxygen in an inverted geometry organic photovoltaic device with emphasis on the accumulated barrier effect of the layers comprising the layer stack. By studying the exchange of oxygen in the zinc oxide (ZnO) layer, the barrier effect is reported in both a dry oxygen atmosphere and an oxygen-free humid atmosphere. The devices under study are comprised of a bulk heterojunction formed by poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester sandwiched between a layer of zinc oxide (electron transporting layer) and a layer of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (hole transport layer) and the two electrodes indium tin oxide and silver. Time-of-flight secondary ion mass spectrometry is employed to characterize the accumulated barrier effect. A pronounced barrier effect is observed in the humid atmosphere, correlating well with a long observed lifetime in the same atmosphere.© 2011 Society of Photo-Optical Instrumentation Engineers.