Probing ionic conductivity and electric field screening in perovskite solar cells: a novel exploration through ion drift currents†

Abstract

It is widely accepted that mobile ions are responsible for the slow electronic responses observed in metal halide perovskite-based optoelectronic devices, and strongly influence long-term operational stability. Electrical characterisation methods mostly observe complex indirect effects of ions on bulk/interface recombination, struggle to quantify the ion density and mobility, and are typically not able to fully quantify the influence of the ions upon the bulk and interfacial electric fields. We analyse the bias-assisted charge extraction (BACE) method for the case of a screened bulk electric field, and introduce a new characterisation method based on BACE, termed ion drift BACE. We reveal that the initial current density and current decay dynamics depend on the ion conductivity, which is the product of ion density and mobility. This means that for an unknown high ion density, typical in perovskite solar absorber layers, the mobility cannot be directly obtained from BACE measurements. We derive an analytical model to illustrate the relation between current density, conductivity and bulk field screening, supported by drift–diffusion simulations. By measuring the ion density independently with impedance spectroscopy, we show how the ion mobility can be derived from the BACE ion conductivity. We highlight important differences between the low- and high-ion density cases, which reveal whether the bulk electric field is fully screened or not. Our work clarifies the complex ion-related processes occurring within perovskite solar cells and gives new insight into the operational principles of halide perovskite devices as mixed ionic–electronic conductors.