Role of Electronic States and Their Coupling on Radiative Losses of Open-Circuit Voltage in Organic Photovoltaics.

Voltage losses (Δ) are a crucial limitation for the performance of excitonic organic solar cells (OSCs) and can be estimated by two approaches─the radiative limit and the Marcus charge-transfer (MCT) model. In this work, we show that combining the radiative limit and MCT models for voltage loss calculations provides useful insights into the physics of emerging efficient OSCs. We studied nine different donor-acceptor systems, wherein the power conversion efficiency ranges from 4.4 to 14.1% and Δ varies from 0.55 to 0.95 V. For these state-of-the-art devices, we calculated the Δ using the radiative limit and the MCT model. Furthermore, we combined both models to derive new insights on the origin of radiative voltage losses (Δ) in OSCs. We quantified the contribution in Δ due to the bulk intramolecular (S) disorder and interfacial intermolecular (CT) disorder by revisiting the spectral regions of interest for OSCs. Our findings are in agreement with the expected relationship of with Urbach energy (), which suggests that the low is beneficial for reduced losses. However, unprecedentedly, we also identify a universal, almost linear relationship between the interfacial disorder (λ) and Δ. We believe that these results can be exploited by the organic photovoltaic (OPV) community for the design of new molecules and a combination of donor-acceptors to further improve OSCs.