Abstract

Previous studies have reported contradictory effects of small-molecule acceptors on the environmental stability of polymer:small-molecule blends, with one showing that a small-molecule acceptor stabilizes and another showing that it destabilizes the polymer donor. In this work, to investigate the origin of these contradictory results, the effects of the nanomorphologies of small-molecule acceptors on the environmental stability of polymer:small-molecule blends are demonstrated. Investigations on the environmental stabilities of polymer:fullerene blends of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7):phenyl-C61-butyric acid methyl ester (PCBM) with contrasting nanomorphologies of PCBM reveal that dispersed PCBM in a mixed phase is the critical factor that causes triplet-mediated singlet oxygen generation and, hence, the severe photooxidation of PTB7, whereas an aggregated PCBM phase stabilizes PTB7 by reducing the formation of PTB7 triplet excitons. In addition, the photooxidation of PTB7 substantially degrades hole transport in the PTB7:PCBM blends by destroying the crystalline PTB7 phases within the films; this effect is strongly correlated with the efficiency losses of the PTB7:PCBM organic solar cells. These conclusions are also extended to polymer:nonfullerene blends of PTB7:ITIC and PTB7:Y6, thereby confirming the generality of this phenomenon for polymer:small-molecule organic solar cells.

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