Effects of High Temperature and Thermal Cycling on the Performance of Perovskite Solar Cells: Acceleration of Charge Recombination and Deterioration of Charge Extraction

In this work, we investigated the effects of high operating temperature and thermal cycling on the photovoltaic performance of perovskite solar cells (PSCs) with a typical mesostructured (m)-TiO2-CH3NH3PbI3-xClx-spiro-OMeTAD architecture. After carrying out temperature-dependent grazing incidence wide-angle X-ray scattering (GIWAXS), in-situ X-ray diffraction (XRD) and optical absorption experiments, thermal durability of PSCs was tested by subjecting the devices to repetitive heating to 70 °C and cooling to room temperature (20 °C). An unexpected regenerative effect was observed after the first thermal cycle; the average power conversion efficiency (PCE) increased by approximately 10 % in reference to the as-prepared device. This increase of PCE was attributed to the heating-induced improvement of crystallinity and p-doping in the hole-transporter, Spiro-OMeTAD, which promotes the efficient extraction of photo-generated carriers. However, further thermal cycles produced a detrimental effect on the photovoltaic performance of PSCs with short-circuit current and fill factor degrading faster than the open-circuit voltage. Similarly, the photovoltaic performance of PSCs degraded at high operation temperatures; both short-circuit current and open-circuit voltage decreased with increasing temperature, but the temperature-dependent trend of fill factor was opposite. Our impedance spectroscopy analysis revealed a monotonous increase of charge transfer resistance and a concurrent decrease of charge recombination resistance with increasing temperature, indicating high recombination of charge carriers. Our results revealed that both thermal cycling and high temperatures produce irreversible detrimental effects on the PSC performance due to the deteriorated interfacial photo-carrier extraction. The present findings suggest that development of robust charge transporters and proper interface engineering are critical for the deployment of perovskite photovoltaics in harsh thermal environments.