AbstractIn an endeavor to understand why the dissociation of charge‐transfer (CT) states in a PM6:Y6 solar‐cell is not a thermally activated process, measurements of energy‐resolved impedance as well as of intrinsic photoconduction are employed. This study determines the density of states distributions of the pertinent HOMO and LUMO states and obtains a Coulomb binding energy (Eb,CT) of ≈150 meV. This is 250 meV lower than the value expected for a pair of localized charges with 1 nm separation. The reason is that the hole is delocalized in the polymer and the electron is shared among Y6 molecules forming a J‐like aggregate. There are two key reasons why this binding energy of the CT state is not reflected in the temperature dependence of the photocurrent of PM6:Y6‐diode: i) The e–h dissociation in a disordered system is a multi‐step process whose activation energy is principally different from the binding energy of the CT state and can be substantially less than Eb,CT, and ii) since dissociation of the CT state competes with its intrinsic decay, the dissociation yield saturates once the rate of dissociation grossly exceeds the rate of intrinsic decay. This study argues that these conditions are met in a PM6:Y6‐solar cell.
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