ABSTRACT:We reveal some of the key mechanisms during charge generation in polymer:fullerene blends exploiting our well-defined understanding of the microstructures obtained in pBTTT:PCBM systems via processing with fatty acid methyl ester additives. Based on ultrafast transient absorption, electroabsorption, and fluorescence up-conversion spectroscopy, we find that exciton diffusion through relatively phase-pure polymer or fullerene domains limits the rate of electron and hole transfer, while prompt charge separation occurs in regions where the polymer and fullerene are molecularly intermixed (such as the co-crystal phase where fullerenes intercalate between polymer chains in pBTTT:PCBM). We moreover confirm the importance of neat domains, which are essential to prevent geminate recombination of bound electron−hole pairs. Most interestingly, using an electro-absorption (Stark effect) signature, we directly visualize the migration of holes from intermixed to neat regions, which occurs on the subpicosecond time scale. This ultrafast transport is likely sustained by high local mobility (possibly along chains extending from the co-crystal phase to neat regions) and by an energy cascade driving the holes toward the neat domains.
There has been long-standing debate on how free charges are generated in donor:acceptor blends that are used in organic solar cells, and which are generally comprised of a complex phase morphology, where intermixed and neat phases of the donor and acceptor material co-exist. Here we resolve this question, basing our conclusions on Stark effect spectroscopy data obtained in the absence and presence of externally applied electric fields. Reconciling opposing views found in literature, we unambiguously demonstrate that the fate of photogenerated electron–hole pairs—whether they will dissociate to free charges or geminately recombine—is determined at ultrafast times, despite the fact that their actual spatial separation can be much slower. Our insights are important to further develop rational approaches towards material design and processing of organic solar cells, assisting to realize their purported promise as lead-free, third-generation energy technology that can reach efficiencies over 10%.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.