Solution processing via roll-to-roll (R2R) coating promises a low cost, low thermal budget, sustainable revolution for the production of solar cells. Poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′′′-di(2-octyldodecyl)-2,2′;5′,2′′;5′′,2′′′-quaterthiophen-5,5-diyl)], PffBT4T-2OD, has recently been shown to achieve high power conversion efficiency (>10%) paired with multiple acceptors when thick films are spun-coat from hot solutions. We present detailed morphology studies of PffBT4T-2OD based bulk heterojunction films deposited by the volume manufacturing compatible techniques of blade-coating and slot-die coating. Significant aspects of the film morphology, the average crystal domain orientation and the distribution of the characteristic phase separation length scales, are remarkably different when deposited by the scalable techniques vs. spun-coat. Yet, we find that optimized blade-coated devices achieve PCE > 9.5%, nearly the same as spun-coat. These results challenge some widely accepted propositions regarding what is an optimal BHJ morphology and suggest the hypothesis that diversity in the morphology that supports high performance may be a characteristic of manufacturable systems, those that maintain performance when coated thicker than ≈200 nm. In situ measurements reveal the key differences in the solidification routes for spin- and blade-coating leading to the distinct film structures.

In this report, we demonstrate that solution-processed amorphous zinc oxide (a-ZnO) interlayers prepared at low temperatures (∼100 °C) can yield inverted bulk-heterojunction (BHJ) solar cells that are as efficient as nanoparticle-based ZnO requiring comparably more complex synthesis or polycrystalline ZnO films prepared at substantially higher temperatures (150–400 °C). Low-temperature, facile solution-processing approaches are required in the fabrication of BHJ solar cells on flexible plastic substrates, such as PET. Here, we achieve efficient inverted solar cells with a-ZnO buffer layers by carefully examining the correlations between the thin film morphology and the figures of merit of optimized BHJ devices with various polymer donors and PCBM as the fullerene acceptor. We find that the most effective a-ZnO morphology consists of a compact, thin layer with continuous substrate coverage. In parallel, we emphasize the detrimental effect of forming rippled surface morphologies of a-ZnO, an observation which contrasts with results obtained in polycrystalline ZnO thin films, where rippled morphologies have been reported to improve efficiency. After optimizing the a-ZnO morphology at low processing temperature for inverted P3HT:PCBM devices, achieving a power conversion efficiency (PCE) of ca. 4.1%, we demonstrate inverted solar cells with low bandgap polymer donors on glass/flexible PET substrates: PTB7:PC₇₁BM (PCE: 6.5% (glass)/5.6% (PET)) and PBDTTPD:PC₇₁BM (PCE: 6.7% (glass)/5.9% (PET)). Finally, we show that a-ZnO based inverted P3HT:PCBM BHJ solar cells maintain ca. 90–95% of their initial PCE even after a full year without encapsulation in a nitrogen dry box, thus demonstrating excellent shelf stability. The insight we have gained into the importance of surface morphology in amorphous zinc oxide buffer layers should help in the development of other low-temperature solution-processed metal oxide interlayers for efficient flexible solar cells.