Effects of energetic disorder and mobility anisotropy on geminate electron-hole recombination in the presence of a donor-acceptor heterojunction

Abstract

Geminate electron-hole recombination in organic solids in the presence of a donor-acceptor heterojunction is studied by computer simulations. We analyze how the charge-pair separation probability in such systems is affected by energetic disorder of the media, anisotropy of charge-carrier mobilities, and other factors. We show that in energetically disordered systems the effect of heterojunction on the charge-pair separation probability is stronger than that in idealized systems without disorder. We also show that a mismatch between electron and hole mobilities reduces the separation probability, although in energetically disordered systems this effect is weaker compared to the case of no energetic disorder. We demonstrate that the most important factor that determines the charge-pair separation probability is the ratio of the sum of electron and hole mobilities to the rate constant of recombination reaction. We also consider systems with mobility anisotropy and calculate the electric field dependence of the charge-pair separation probability for all possible orientations of high-mobility axes in the donor and acceptor phases. We theoretically show that it is possible to increase the charge-pair separation probability by controlling the mobility anisotropy in heterojunction systems and in consequence to achieve higher efficiencies of organic photovoltaic devices.