Analysis of the photovoltaic efficiency of a molecular solar cell based on a two-level system

A molecular solar cell is modelled as a two-level system connected to electrodes by chains of electron-transporting and hole-transporting orbitals. Light absorption and emission are simulated using the generalised Planck equation and intermolecular charge transfer using non-adiabatic Marcus theory. Quantum efficiency-voltage characteristics, open-circuit voltage and monochromatic power-conversion efficiency are calculated as a function of the following parameters: charge-separation rate, interfacial recombination rate, charge mobility, light intensity and built-in bias. We find that slow charge separation, fast recombination and low mobility all contribute to a decrease in efficiency compared to the ideal (detailed balance) limit. When charge-separation and interfacial recombination rates are related through the intermolecular coupling, maximum efficiency is achieved at some optimum, but not the maximum, charge-separation rate. Two regimes are distinguished for the open-circuit voltage: when interfacial recombination is important, V-oc varies approximately linearly with the donor-acceptor energy gap; but when recombination is insignificant, V-oc is determined by the optical gap. Including exciton binding energy in the driving force for charge separation reduces V-oc. In systems with significant recombination, V-oc first increases and then saturates with increasing light intensity. Low mobility and interfacial recombination are the main avoidable sources of loss when realistic parameters are used, but the effects of low mobility can be partly compensated by applying a built-in bias between the electrodes.