Suppressing photooxidation of conjugated polymers and their blends with fullerenes through nickel chelates

Conjugated polymer semiconductors offer unique advantages over conventional semiconductors but tend to suffer from electro-optic performance roll-off, mainly due to reduced photofastness. Here, we demonstrate that the commodity nickel chelate nickel(ii) dibutyldithiocarbamate, Ni(dtc), effectively inhibits photooxidation across a wide range of prototypical π-conjugated polymer semiconductors and blends. The addition of 2-10 wt% of Ni(dtc) increases the resilience of otherwise quickly photobleaching semiconducting thin films, even in the presence of detrimental, radical forming processing additives. Using electron spin resonance spectroscopy and sensitive oxygen probes, we found that Ni(dtc) acts as a broadband stabilizer that inhibits both the formation of reactive radicals and singlet oxygen. The mechanism of stabilization is of sacrificial nature, but contains non-sacrificial contributions in polymers where singlet oxygen is a key driver of photooxidation. Ultrafast pump-probe spectroscopy reveals quenching of triplet excited states as the central mechanism of non-sacrificial stabilization. When introduced into the active layer of organic photovoltaic devices, Ni(dtc) retards the short circuit current loss in air without affecting the sensitive morphology of bulk heterojunctions and without major sacrifices in semiconductor properties. Antioxidants based on nickel complexes thus constitute functional stabilizers for elucidating degradation mechanisms in organic semiconductors and represent a cost-effective route toward organic electronic appliances with extended longevity.