Entropy and Disorder Enable Charge Separation in Organic Solar Cells.

Although organic heterojunctions can separate charges with near-unity efficiency and on a subpicosecond time scale, the full details of the charge-separation process remain unclear. In typical models, the Coulomb binding between the electron and the hole can exceed the thermal energy kB T by an order of magnitude, suggesting that it is impossible for the charges to separate before recombining. Here, we consider the entropic contribution to charge separation in the presence of disorder and find that even modest amounts of disorder have a decisive effect, reducing the charge-separation barrier to about kB T or eliminating it altogether. Therefore, the charges are usually not thermodynamically bound at all and could separate spontaneously if the kinetics otherwise allowed it. Our conclusion holds despite the worst-case assumption of localized, thermalized carriers and is only strengthened if mechanisms like delocalization or "hot" states are also present.