High-efficiency small-molecule ternary solar cells with a hierarchical morphology enabled by synergizing fullerene and non-fullerene acceptors

Using combinatory photoactive blends is a promising approach to achieve high power conversion efficiency in ternary organic photovoltaics. However, the fundamental challenge of how to manipulate the morphology of multiple components and correlate structure details via device performance has not been well addressed. Achieving an ideal morphology that simultaneously enhances charge generation and transport and reduces voltage loss is an imperative avenue to improve device efficiency. Here, we achieve a high power conversion efficiency of 13.20 +/- 0.25% for ternary solar cells by using a combination of small molecules with both fullerene and non-fullerene acceptors, which form a hierarchical morphology consisting of a PCBM transporting highway and an intricate non-fullerene phase-separated pathway network. Carrier generation and transport find an optimized balance, and voltage loss is simultaneously reduced. Such a morphology fully utilizes the individual advantages of both fullerene and non-fullerene acceptors, demonstrating their indispensability in organic photovoltaics.