Transparent and Conductive Polyimide‐Ionene Hybrid Interlayers for High Performance and Cost‐Effective Semitransparent Organic Solar Cells

Abstract The contradiction between high transmittance and favorable conductivity poses a great challenge in developing effective cathode interlayer (CIL) materials with sufficient thickness tolerance, which hinders the further advancement of organic solar cells (OSCs). Herein, a completely new class of alcohol processable polyimide‐ionene hybrids (PIIHs) is proposed by melding pyromellitic diimide (PMD) subunits into imidazolium‐based ionenes backbone covalently. These PIIHs, named PMD‐DI and PMD‐PD, boast high transparency, suitable energy levels, and decent conductivity. A higher PMD content endows PMD‐PD with improved work function tunability, electrical properties, and crystallinity, enabling PMD‐PD as CIL material with excellent thickness‐insensitive characteristics, while simultaneously improving device stability significantly. Furthermore, PMD‐PD also exhibits good compatibility with various electrodes and active layers, offering solar cell efficiencies of up to 19.91% and 19.29% with Ag and Cu cathodes, respectively. More importantly, the application of PMD‐PD can improve the performance of semi‐transparent OSCs without losing transmittance, thereby drastically enhancing the light utilization efficiency to 4.04% with an ultrathin, low‐cost Cu cathode, that competes with leading optical modulation‐free semitransparent OSCs with expensive Ag cathodes. This work opens a pathway to realize transparent and conductive interlayers by strategic molecular design, leading to highly efficient, stable, and cost‐effective OSCs suitable for diverse applications.