The kinetics of photodegradation and the reactivity of different sites of the low-band-gap polymers 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) are investigated as thin films and are compared to those of poly(3-hexylthiophene) (P3HT). The decay kinetics are monitored with UV/Vis spectroscopy and the reactivity and product evolution are investigated with X-ray photoelectron spectroscopy (XPS). Both polymers exhibit higher stability than P3HT. The bridging atom in the cyclopentadithiophene (CPDT) subunit has a significant influence on the stability. Varying oxidation rates for the different elements were observed. In the case of Si-PCPDTBT, the silicon atom is oxidized primarily, whereas the photooxidation rates of the other elements are reduced relative to C-PCPDTBT. Additionally, XPS experiments with varying excitation energies reveal a significant reaction gradient within a few nanometers of the surface of degraded thin films of C-PCPDTBT.
Keywords: degradation; low-band-gap polymers; organic solar cells; photoelectron spectroscopy; photooxidation.
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