We monitored the evolution in time of pinhole-free structures based on FTO/TiO/CHNHPbICl layers, with and without spiro-OMeTAD and counter electrodes (Ag, Mo/Ag, and Au), aged at 24 °C in a dark nitrogen atmosphere. In the absence of electrodes, no degradation occurs. While devices with Au show only a 10% drop in power conversion efficiency, remaining stable after a further overheating at 70 °C, >90% is lost when using Ag, with the process being slower for Mo/Ag. We demonstrate that iodine is dislocated by the electric field between the electrodes, and this is an intrinsic cause for electromigration of I from the perovskite until it reaches the anode. The iodine exhaustion in the perovskite layer is produced when using Ag electrodes, and AgI is formed. We hypothesize that in the presence of Au the iodine migration is limited due to the buildup of I negative space charge accumulated at the perovskite-OMeTAD interface.

Hysteretic effects are investigated in perovskite solar cells in the standard FTO/TiO2/CH3NH3PbI3−xClx/spiro-OMeTAD/Au configuration.We report normal (NH) and inverted hysteresis (IH) in the J-V characteristics occurring for the same device structure, the behavior strictly depending on the pre-poling bias. NH typically appears at pre-poling biases larger than the open circuit bias, while pronounced IH occurs for negative bias pre-poling. The transition from NH to IH is marked by a intermediate mixed hysteresis behavior characterized by a crossing point in the J-V characteristics. The measured J-V characteristics are explained quantitatively by the dynamic electrical model (DEM). Furthermore, the influence of the bias scan rate on the NH/IH hysteresis is discussed based on the time evolution of the non-linear polarization. Introducing a three step measurement protocol, which includes stabilization, pre-poling and measurement, we put forward the difficulties and possible solutions for a correct PCE evaluation.

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The short-circuit photocurrent was measured in ferroelectric capacitors of polycrystalline and epitaxial quality. The interest was to study the possible relation between photocurrent and back-switching phenomena due to ferroelectric polarization imprint, as suggested by Pintilie et al. [J. Appl. Phys. 101, 064109 (2007)]. An interesting relation between the shape of the ferroelectric hysteresis loop and the shape of the photocurrent spectral distribution was found. In polycrystalline samples, the shape of spectral distribution and the sign of photocurrent are changing in time, although the hysteresis is almost symmetrical. However, the hysteresis is not rectangular as in the case of epitaxial films. This behavior suggests a subtle relation between polarization back-switching and photocurrent. In epitaxial samples a peculiar dependence between photocurrent and polarization imprint was found. All these are explained assuming the presence of an internal field, possibly generated by charged defects, which can change its direction and magnitude under illumination, with consequence on the orientation and magnitude of the ferroelectric polarization, and on the sign/shape of the short-circuit photocurrent spectral distribution.