Solvent Additives: Key Morphology‐Directing Agents for Solution‐Processed Organic Solar Cells

Abstract Organic photovoltaics (OPV) have the advantage of possible fabrication by energy‐efficient and cost‐effective deposition methods, such as solution processing. Solvent additives can provide fine control of the active layer morphology of OPVs by influencing film formation during solution processing. As such, solvent additives form a versatile method of experimental control for improving organic solar cell device performance. This review provides a brief history of solution‐processed bulk heterojunction OPVs and the advent of solvent additives, putting them into context with other methods available for morphology control. It presents the current understanding of how solvent additives impact various mechanisms of phase separation, enabled by recent advances in in situ morphology characterization. Indeed, understanding solvent additives' effects on film formation has allowed them to be applied and combined effectively and synergistically to boost OPV performance. Their success as a morphology control strategy has also prompted the use of solvent additives in related organic semiconductor technologies. Finally, the role of solvent additives in the development of next‐generation OPV active layers is discussed. Despite concerns over their environmental toxicity and role in device instability, solvent additives remain relevant morphological directing agents as research interests evolve toward nonfullerene acceptors, ternary blends, and environmentally sustainable solvents.