Abstract
Surface modification of indium tin oxide (ITO)‐coated substrates through the use of self‐assembled monolayers (SAMs) of molecules with permanent dipole moments has been used to control the anode work function and device performance in molecular solar cells based on a CuPc:C~60~ (CuPc: copper phthalocyanine) heterojunction. Use of SAMs increases both the short‐circuit current density (J~sc~) and fill factor, increasing the power‐conversion efficiency by up to an order of magnitude. This improvement is attributed primarily to an enhanced interfacial charge transfer rate at the anode, due to both a decrease in the interfacial energy step between the anode work function and the highest occupied molecular orbital (HOMO) level of the organic layer, and a better compatibility of the SAM‐modified electrodes with the initial CuPc layers, which leads to a higher density of active sites for charge transfer. An additional factor may be the influence of increasing electric field at the heterojunction on the exciton‐dissociation efficiency. This is supported by calculations of the electric potential distribution for the structures. Work‐function modification has virtually no effect on the open‐circuit voltage (V~oc~), in accordance with the idea that V~oc~ is controlled primarily by the energy levels of the donor and acceptor materials.