The impact of spiro-OMeTAD photodoping on the reversible light-induced transients of perovskite solar cells

Hole transporting materials (HTMs) play essential roles in facilitating hole extraction and suppressing recombination in lead halide perovskite solar cells (PSCs). High levels of p-doping in HTMs is necessary for achieving high device performance, attributed to an increased electrical conductivity. In this work, we provide evidences that the poor performance of PSCs with low levels of doping (i.e., 4 mol% spiro-OMeTAD+) in spiro-OMeTAD is mainly caused by the presence of a Schottky barrier at the perovskite/spiro-OMeTAD interface, hampering hole injection. Under continuous illumination at open-circuit condition, the barrier gradually diminishes, increasing the PSC power conversion efficiency by 70-fold after 7 h. This process is completely reversible, returning to the initial poor performance after dark storage. We attribute this improvement in performance to a gradual photodoping of spiro-OMeTAD, triggered by the transfer of photogenerated holes and mediated by the slow migration of halide anions from perovskite to compensate the newly formed spiro-OMeTAD+. In-situ parallel analyses with impedance spectroscopy (IS) and photoluminescence are employed to gain insights into the charge dynamics along with light soaking. We find that the Schottky barrier resistance overlays with the recombination signal at the high frequency arc of IS, having important implications for the IS data analysis for PSCs. The work elucidates a major mechanism causing the slow efficiency variations during light/dark cycling, commonly observed in PSCs, which complicates the determination of long-term stability.