Ohmic transition at contacts key to maximizing fill factor and performance of organic solar cells

While thermodynamic detailed balance limits the maximum power conversion efficiency of a solar cell, the quality of its contacts can further limit the actual efficiency. The criteria for good contacts to organic semiconductors, however, are not well understood. Here, by tuning the work function of poly(3,4-ethylenedioxythiophene) hole collection layers in fine steps across the Fermi-level pinning threshold of the model photoactive layer, poly(3-hexylthiophene):phenyl-C₆₁-butyrate methyl ester, in organic solar cells, we obtain direct evidence for a non-ohmic to ohmic transition at the hole contact that lies 0.3 eV beyond its Fermi-level pinning transition. This second transition corresponds to reduction of the photocurrent extraction resistance below the bulk resistance of the cell. Current detailed balance analysis reveals that this extraction resistance is the counterpart of injection resistance, and the measured characteristics are manifestations of charge carrier hopping across the interface. Achieving ohmic transition at both contacts is key to maximizing fill factor without compromising open-circuit voltage nor short-circuit current of the solar cell.