Sub-bandgap Photocurrent Spectra of p-i-n Perovskite Solar Cells with n-Doped Fullerene Electron Transport Layers and Bias Illumination

In p-i-n perovskite solar cells optical excitation of defect states at the interface between the perovskite and fullerene electron transport layer (ETL) creates a photocurrent responsible for a distinct sub-bandgap external quantum efficiency (EQE). The precise nature of these signals and their impact on cell performance are largely unknown. Here, the effect of n-doping the fullerene on the EQE spectra is studied. The n-doped fullerene is either deposited from solution or by coevaporation. The latter method is used to create undoped-doped fullerene bilayers and investigate the effect of the proximity of the doped region on the EQE spectra. The intensity of the sub-bandgap EQE increases when the ETL is n-doped and also when the device is biased with green light. Using these results, the sub-bandgap EQE signal is attributed to originate from electron trap states in the perovskite with an energy below the conduction band that are filled by excitation with low-energy photons. The trapped electrons give rise to photocurrent when they are collected at a nearby electrode. The enhanced sub-bandgap EQE observed when the ETL is n-doped or bias light is applied, is related to a higher probability to extract trapped electrons under these conditions.