Orthogonal Printable Reduced Graphene Oxide 2D Materials as Hole Transport Layers for High-Performance Inverted Polymer Solar Cells: Sheet Size Effect on Photovoltaic Properties

Creating an orthogonal printable hole-transporting layer (HTL) without damaging the underlying layer is still a major challenge in fabricating large-area printed inverted polymer solar cells (PSCs). In this study, we prepared orthogonal-processable fluorine-functionalized reduced graphene oxide (FrGO) series with various two-dimensional sheet sizes such as large-sized FrGO (1.1 μm), medium-sized FrGO (0.7 μm), and small-sized FrGO (0.3 μm) and systematically investigated the size effect of FrGOs on the hole transport properties of PSCs. The FrGOs exhibit highly stable dispersion without change over 90 days in 2-propanol solvent, indicating very high dispersion stability. Decreasing the sheet size of FrGOs enhanced hole-transporting properties, resulting in power conversion efficiencies (PCEs) of 9.27 and 9.02% for PTB7-Th:EH-IDTBR- and PTB7-Th:PC₇₁BM-based PSCs, respectively. Compared to devices with solution-processed poly­(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a 14% enhancement of PCEs was achieved. Interestingly, the PCEs of devices with the smallest FrGO sheet are higher than the PCE of 8.77% of a device with vacuum-deposited MoO₃. The enhancement in the performance of PSCs is attributed to the enhanced charge collection efficiency, decreased leakage current, internal resistance, and minimized charge recombination. Finally, small-sized FrGO HTLs were successfully coated on the photoactive layer using the spray coating method, and they also exhibited PCEs of 9.22 and 13.26% for PTB7-Th:EH-IDTBR- and PM6:Y6-based inverted PSCs, respectively.