Nonequilibrium Thermodynamics of Charge Separation in Organic Solar Cells

This work presents a novel theoretical description of the nonequilibrium thermodynamics of charge separation in organic solar cells (OSCs). Using stochastic thermodynamics, we take realistic state populations derived from the phonon-assisted dynamics of electron-hole pairs within photoexcited organic bilayers to connect the kinetics with the free energy profile of charge separation. Hereby, we quantify for the first time the difference between nonequilibrium and equilibrium free energy profile. We analyze the impact of energetic disorder and delocalization on free energy, average energy, and entropy. For a high disorder, the free energy profile is well-described as equilibrated. We observe significant deviations from equilibrium for delocalized electron-hole pairs at a small disorder, implying that charge separation in efficient OSCs proceeds via a cold but nonequilibrated pathway. Both a large Gibbs entropy and large initial electron-hole distance provide an efficient charge separation, while a decrease in the free energy barrier does not necessarily enhance charge separation.

Automated summary

This work presents a novel theoretical description of the nonequilibrium thermodynamics of charge separation in organic solar cells, quantifying for the first time the difference between nonequilibrium and equilibrium free energy profiles. The study reveals that charge separation in efficient OSCs proceeds via a cold but nonequilibrated pathway for delocalized electron-hole pairs at a small disorder, with large Gibbs entropy and initial electron-hole distance contributing to efficient charge separation.