New small molecules having modified acceptor strength and π-conjugation length and containing dicyanovinylene (DCV) and tricyanovinylene (TCV) as a strongly electron-accepting unit with indacenodithiophene, IDT(DCV), IDT(TCV), and IDTT(TCV), were synthesized and studied in terms of their applicability to polymer solar cells with PTB7-Th as an electron-donating polymer. Intriguingly, the blended films containing IDT(TCV) and IDTT(TCV) exhibited superior shelf life stabilities of more than 1000 h without any reduction in the initial power conversion efficiency. The low-lying lowest unoccupied molecular orbital energy levels and robust internal morphologies of small TCV-containing molecules could afford excellent shelf life stability.
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