LAUSR

The long-range ordering of bulk-heterojunctions (BHJs) significantly facilitates exciton diffusion and dissociation as well as charge transport. A feasible bio-inspired strategy to realize such a heterostructure is crystallization in gel media where the growing host crystals incorporate the surrounding guest materials of gel networks. Until now, the host-guest pairs forming ordered BHJs are still very limited and, more importantly, the used gel-network guests are structurally amorphous, spurring investigation toward crystalline gel-networks. Here, single crystals of fullerene and non-fullerene acceptors (NFAs) in poly(3-hexylthiophene) (P3HT) organogel are prepared, forming C60 :P3HT and (5Z,5″Z)-5,5″-((7,7″-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b″]dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene))bis(3-ethyl-2-thioxothiazolidin-4-one) (O-IDTBR):P3HT BHJs. The crystalline P3HT network penetrates the crystal matrix without significantly disturbing the single crystallinity, resulting in long-range ordered BHJs. This bi-continuous structure, together with an improved overall ordering, contributes to enhanced charge/energy transfer. As a result, photodetectors based on these ordered BHJs exhibit ameliorated responsivity, detectivity, bandwidth, and stability as compared to the conventional BHJs with short-range ordering. Therefore, this work further extends the scope of long-range ordered BHJs toward crystalline polymer donors and NFAs, providing a generally applicable strategy for the design of organic optoelectronic devices with superior performance.