Overcoming Transport Layer Bottlenecks to Quantify Ionic Parameters from Transient Ion Current Measurements of Perovskite Solar Cells

Abstract

In perovskite solar cells (PSCs), voltage step-induced transient ion current (TIC) measurements, commonly referred to as bias-assisted charge extraction (BACE), are frequently used to quantify ion density. Drift-diffusion simulations predict that the ion density computed from TIC saturates once mobile ions screen the electric field in the perovskite. However, experimental studies often report ion densities orders of magnitude above this limit, whose physical origin remains incompletely explained in terms of transport layer (TL) properties. In this work, the capacitance of the TLs is identified to be the fundamental bottleneck: the maximum quantifiable ion density is limited to the charge that can accumulate at the perovskite/TL interfaces, so that TIC most often depends more strongly on TL properties than on the ionic properties of the perovskite. Experiments with systematically varied C$_{\rm 60}$ electron-TL thickness (p-i-n) and Spiro-OMeTAD hole-TL doping (n-i-p) confirm this dependence across architectures. To overcome this limitation, the importance of a correction based on the average ionic displacement is discussed, and it is shown how extrapolating the TL-thickness trend towards the TL-free situation yields the actual ionic conductivity of the absorber, alongside density and mobility, depending on the assumed ionic model. Simulations are also examined in which ion penetration into the TLs or initial accumulation under forward bias raise the capacitive limit and extend TIC sensitivity to higher ion densities. The slow release of trapped carriers is also discussed as a potential source of current which can inflate the TIC signal. Overall, the presented analysis provides important practical considerations for interpreting TIC and quantifying ionic properties in PSCs.