Direct observation of charge transfer at the interface between PEDOT:PSS and perovskite layers

Although the interface between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and perovskite layers is one of the key factors to determine the open-circuit voltage of inverted perovskite solar cells, this interface remains poorly understood. We investigated the interface by electron spin resonance spectroscopy and found that the PEDOT undergoes dedoping in contact with the perovskite. The holes in PEDOT were reduced by electron transfer from the perovskite. Additional electron transfer occurred upon light irradiation. The electron transfer would be related to lower open-circuit voltages of the inverted structure compared to those of mesoporous and planar structures.