Charge-Transfer State Dissociation Efficiency Can Limit Free Charge Generation in Low-Offset Organic Solar Cells

[Image: see text] We investigate the charge-generation processes limiting the performance of low-offset organic bulk-heterojunction solar cells by studying a series of newly synthesized PBDB-T-derivative donor polymers whose ionisation energy (IE) is tuned via functional group (difluorination or cyanation) and backbone (thiophene or selenophene bridge) modifications. When blended with the acceptor Y6, the series present heterojunction donor–acceptor IE offsets (ΔE(IE)) ranging from 0.22 to 0.59 eV. As expected, small ΔE(IE) decrease nonradiative voltage losses but severely suppresses photocurrent generation. We explore the origin of this reduced charge-generation efficiency at low ΔE(IE) through a combination of opto-electronic and spectroscopic measurements and molecular and device-level modeling. We find that, in addition to the expected decrease in local exciton dissociation efficiency, reducing ΔE(IE) also strongly reduces the charge transfer (CT) state dissociation efficiency, demonstrating that poor CT-state dissociation can limit the performance of low-offset heterojunction solar cells.