Revealing defective interfaces in perovskite solar cells from highly sensitive sub-bandgap photocurrent spectroscopy using optical cavities

Defects in perovskite solar cells are known to affect the performance, but their precise nature, location, and role remain to be firmly established. Here, we present highly sensitive measurements of the sub-bandgap photocurrent to investigate defect states in perovskite solar cells. At least two defect states can be identified in p-i-n perovskite solar cells that employ a polytriarylamine hole transport layer and a fullerene electron transport layer. By comparing devices with opaque and semi-transparent back contacts, we demonstrate the large effect of optical interference on the magnitude and peak position in the sub-bandgap external quantum efficiency (EQE) in perovskite solar cells. Optical simulations reveal that defects localized near the interfaces are responsible for the measured photocurrents. Using optical spacers of different lengths and a mirror on top of a semi-transparent device, allows for the precise manipulation of the optical interference. By comparing experimental and simulated EQE spectra, we show that sub-bandgap defects in p-i-n devices are located near the perovskite-fullerene interface. Sensitive photocurrent spectroscopy and interference of light in perovskite solar cells with optical spacers reveal that electronic defects in these devices are localized at the interface between the semiconductor and the electron collecting contact.