Measuring Temperature-Dependent Miscibility for Polymer Solar Cell Blends: An Easily Accessible Optical Method Reveals Complex Behavior

In bulk-heterojunction polymer solar cells (PSC), the molecular-level mixing between conjugated polymer donors and small-molecule acceptors plays a crucial role in obtaining a desirable morphology and good device stability. It has been recently shown that the thermodynamic limit of this mixing can be quantified by the liquidus miscibility, the composition of the small-molecule acceptor in amorphous phases in the presence of small-molecule crystals, and then converted to the Flory–Huggins interaction parameter χ. This conversion maps out the amorphous miscibility. Moreover, the quantitative relations between χ and the fill factor of PSC devices were established recently. However, the commonly used measurement of this liquidus miscibility, scanning transmission X-ray microscopy, is not easily and readily accessible. Here, we delineate a method based on common visible light microscopy and ultraviolet–visible absorption spectroscopy to replace the X-ray measurements. To demonstrate the feasibility of this technique and methodology, a variety of conjugated polymers (PffBT4T-C 9 C 13, PDPP3T PBDT-TS1, PTB7-Th, and FTAZ) and their miscibility with fullerenes or nonfullerene small molecules (PC 71 BM, PC 61 BM, and EH-IDTBR) are characterized. The establishment of this methodology will pave the way to a wider use of the liquidus miscibility and the critical miscibility-function relations to optimize the device performance and obtain good stability in PSCs and other devices.