Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset

TL;DR

This study uses a 3D delocalised kinetic Monte Carlo model to show that charge generation in organic photovoltaics is highly efficient even with minimal energetic offset, due to delocalisation effects.

Contribution

The paper introduces a comprehensive 3D model incorporating disorder, delocalisation, and polaron formation, revealing how delocalisation enhances charge separation without large energetic offsets.

Findings

Delocalisation significantly boosts charge-generation efficiency.

Efficient charge separation occurs even in neat materials with little to no offset.

Faster, longer-distance hops between delocalised states facilitate charge separation.

Abstract

Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between the charges, which they must overcome to separate. Separation has been thought to require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation with small offsets, or with none at all in neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) to develop a three-dimensional model of charge generation that includes disorder, delocalisation, and polaron formation in every step from photoexcitation to charge separation. Our simulations show that delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons to dissociate in the bulk. Therefore, charge generation can be efficient even in devices with little to no energetic offset, including neat materials. Our findings demonstrate that the underlying quantum-mechanical effect that improves the charge-separation kinetics is faster and longer-distance hops between delocalised states, mediated by hybridised states of exciton and charge-transfer character.