Continuous operation of a polymer photovoltaic device under accelerated conditions for more than 1 year has been demonstrated (8760h at 72 degrees C, 1000Wm(-2), AM 1.5, under vacuum). Formation of hydrogen-bonded networks is proposed to be responsible for the long lifetime and high stability observed in photovoltaic devices employing polythiophene substituted with carboxylic-acid moieties under oxygen free conditions. (1)H and (13)C solid-state NMR, IR, and ESR spectroscopy of unmodified and isotopically labeled polythiophenes were studied. Distances between the isotopically labeled carboxylic acid carbon atoms were measured by (13)C solid-state magic-angle-spinning (MAS) NMR using symmetry-based double-quantum (2Q) dipolar recoupling. This revealed the presence of (13)C-(13)C distances of 3.85 angstrom, which correspond to the C-C distance in hydrogen-bonded carboxylic acid dimers. In spite of the presence of carboxylic groups in the polymer as demonstrated by (13)C CP/MAS NMR and IR spectroscopy, the absence of carboxylic protons in solid state (1)H NMR spectra indicate that they are mobile. We link the extraordinary stability of this system to the rigid nature, cross-linking through a hydrogen-bonded network and a partially oxidized state. (c) 2007 Elsevier B.V. All rights reserved.