Contrasting Effects of Energy Transfer in Determining Efficiency Improvements in Ternary Polymer Solar Cells

Abstract Crystallizable, high‐mobility conjugated polymers have been employed as secondary donor materials in ternary polymer solar cells in order to improve device efficiency by broadening their spectral response range and enhancing charge dissociation and transport. Here, contrasting effects of two crystallizable polymers, namely, PffBT4T‐2OD and PDPP2TBT, in determining the efficiency improvements in PTB7‐Th:PC₇₁BM host blends are demonstrated. A notable power conversion efficiency of 11% can be obtained by introducing 10% PffBT4T‐2OD (relative to PTB7‐Th), while the efficiency of PDPP2TBT‐incorporated ternary devices decreases dramatically despite an enhancement in hole mobility and light absorption. Blend morphology studies suggest that both PffBT4T‐2OD and PDPP2TBT are well dissolved within the host PTB7‐Th phase and facilitate an increased degree of phase separation between polymer and fullerene domains. While negligible charge transfer is determined in binary blends of each polymer mixture, effective energy transfer is identified from PffBT4T‐2OD to PTB7‐Th that contributes to an improvement in ternary blend device efficiency. In contrast, energy transfer from PTB7‐Th to PDPP2TBT worsens the efficiency of the ternary device due to inefficient charge dissociation between PDPP2TBT and PC₇₁BM.