The stability of TiO/CHNHPbICl -based photovoltaic devices in ambient air was evaluated upon adding PbI and/or PbCl. X-ray diffraction (XRD) peak intensities corresponding to the perovskite phase were increased by adding PbI. After 7 weeks, the XRD peak intensities corresponding to the perovskite phase decreased and those corresponding to PbI increased. The reaction rate constants for the decomposition of perovskite and formation of PbI were estimated from these data. Thermodynamic calculations of the reaction between PbCl and I suggested that the formation of PbI was not related to the added PbCl but rather to excess PbI. Open-circuit voltages and fill factors of the devices were improved with the 7 week time lapse because of the suppression of electron-hole recombination by the PbI. In addition, the decomposition of perovskite grains was suppressed by the added PbI. The I content of the perovskite phase decreased with the 7 week time lapse. However, the Cl content was largely constant after the 7 weeks, which suggested that Cl doping effectively stabilized the perovskite photovoltaic devices.
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