Charge dissociation in organic solar cells—from Onsager and Frenkel to modern models

Abstract

Organic-based solar cells have developed for the last three decades. Moving forward generally requires the assistance of useful models that are adapted to currently used materials and device architectures. The least understood part of the charge generation is the first step of the exciton dissociation, and new or refined models are being suggested. However, many of today's questions have been asked before, going back almost an entire century. We have gone to the 1930s and attempted to critically review significant contributions on equal footing. We find that Onsager's and Frenkel's models have a similar foundation but were developed to suit very different materials (ions in solutions vs electrons in semiconductors). The contribution by Braun or the Onsager–Braun model can be considered wrong, yet it was instrumental for the field's development. The community practically ignores one of the most promising models (Arkhipov–Baranovskii). Hot exciton dissociation has many faces due to “hot” being a relative term and/or the heat being stored in different ways (electronic, vibronic, etc.). Entropy considerations are instrumental in simplifying the picture, yet they add no physics compared to the full-3D models. We hope that by emphasizing the physical picture of the various models and the underlying assumptions, one could use them as a stepping stone to the next generation models.