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We studied ion transport in hybrid organic inorganic perovskite p-i-n devices as a function of applied bias under device operating conditions. Using electrochemical impedance spectroscopy (EIS) and equivalent circuit modeling, we elucidated various resistive and capacitive elements in the device. We show that ion migration is predictably influenced by a low applied forward bias, characterized by an increased capacitance at the hole transporting (HTM) and electron transporting material (ETM) interfaces, as well as through the bulk. However, unlike observations in n-i-p devices, we found that there is a capacitive discharge leading to ion redistribution in the bulk at high forward biases. Furthermore, we show that a chemical double layer capacitance buildup as a result of ion accumulation impacts the electronic properties of the device, likely by either inducing charge pinning or charge screening, depending on the direction of the ion induced field. Lastly, we extrapolate ion diffusion coefficients (~10-7 cm2 s-1) and ionic conductivities (~10-7 S cm-1) from the Warburg mass (ion) diffusion response, and show that, as the device degrades, there is an overall depletion of capacitive effects coupled with an increased ion mobility.


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