The numerous assorted accounts of the fundamental questions of ion migration in hybrid perovskites are making the picture further intricate. The review of photo-induced ion migration using small perturbation frequency domain techniques other than impedance spectroscopy is more crucial now. Herein, we probe into this by investigating perovskite–electrolyte (Pe–E) and polymer-aqueous electrolyte (Po–aqE) interface using intensity modulated photocurrent spectroscopy (IMPS) in addition to photoelectrochemical impedance spectroscopy (PEIS). We reported that the electronic-ionic interaction in hybrid perovskites including the low-frequency ion/charge transfer and recombination kinetics at the interface leads to the spiral feature in IMPS Nyquist plot of perovskite-based devices. This spiral trajectory for the perovskite-electrolyte interface depicts three distinct ion kinetics going on at the different time scales which can be more easily unveiled by IMPS rather than PEIS. Hence, IMPS is a promising alternative to PEIS. We used Peter’s method of interpretation of IMPS plot in photoelectrochemistry to estimate charge transfer efficiency $$({Q}_{ste})$$ ( Q ste ) from the Rate Constant Model. The $${Q}_{ste}$$ Q ste at low-frequency for Pe–E interface exceeds unity due to ion migration induced modified potential across the perovskite active layer. Hence, ion migration and mixed electronic-ionic conductivity of hybrid perovskites are responsible for the extraordinary properties of this material.

The numerous assorted accounts to the fundamental questions of ion migration in hybrid perovskites are making the picture further intricate. The review of photo-induced ion migration using small perturbation frequency domain techniques other than impedance spectroscopy is more crucial now. Herein, we probe into this by investigating perovskite-electrolyte (Pe-E) and polymer-aqueous electrolyte (Po-aqE) interface using intensity modulated photocurrent spectroscopy (IMPS) in addition to photoelectrochemical impedance spectroscopy (PEIS). We reported that the electronic-ionic interaction in hybrid perovskites including the low-frequency ion/charge transfer and recombination kinetics at the interface leads to the spiral feature in IMPS Nyquist plot of perovskite-based devices. This spiral trajectory for perovskite-electrolyte interface depicts three distinct ion kinetics going on at the different time scales which can be more easily unveiled by IMPS rather than PEIS. Hence, IMPS is a promising alternative to PEIS. We used Peter’s method of interpretation of IMPS plot in photoelectrochemistry to estimate charge transfer efficiency \(\left({Q}_{ste}\right)\) from the Rate Constant Model. The \({Q}_{ste}\) at low-frequency for Pe-E interface exceeds unity due to ion migration induced modified potential across the perovskite active layer. Hence, ion migration and mixed electronic-ionic conductivity of hybrid perovskites are responsible for the extraordinary properties of this material.