The curious case of ion migration in solid-state and liquid electrolyte-based perovskite devices: unveiling the role of charge accumulation and extraction at the interfaces

Electrochemical impedance spectroscopy (EIS) has been extensively used for the detailed investigation and understanding of the plethora of physical properties of variegated electrochemical and solid-state systems. Over the past few years, EIS has revealed many significant findings in hybrid halide perovskite (HHP)-based optoelectronic devices too. Photoinduced ion-migration, negative capacitance, anomalous mid-frequency capacitance, hysteresis, and instability to heat, light and moisture in HHP-based devices are among the few issues addressed by the IS technique. However, performing EIS in perovskite devices presents new challenges related to multilayer solid-state device geometry and complicated material properties. The ions in the perovskite behave in a specified manner, which is dictated by the energy-levels of the transport layer. Electronic-ionic coupling is one of the major challenges to understand ion transport kinetics in solid-state devices. In this work, we have performed impedance measurements in both solid-state (S-S) and liquid-electrolyte (L-E) device geometry to unfold the effect of charge transport layers on the ac ionic conductivity in perovskite materials. We have modelled the impedance spectra using the electrical equivalent circuit (EEC) and compared the behaviour of ions in different controlling environments. It was concluded that the AC as well as dc ionic conductivity and the accumulation of ions in the perovskite material are highly influenced by the nature of the interface in different device geometry. Charge accumulation in the S-S device gives rise to large polarisation, thereby negative capacitance or any inductive loop can be observed in the Nyquist plot while in the L-E device the presence of an electric double layer at the perovskite/electrolyte interface reduces the surface polarisation effect. Ionic conductivity is hopping limited in the low field regime and diffusion limited in the high field regime in the S-S device. Moreover, the perovskite/electrolyte based devices are promising candidates for electrolyte gated field-effect transistors, perovskite-based supercapacitors and electrochemical cells for water splitting or CO2 reduction.