Mobile Ion-Driven Modulation of Electronic Conductivity Explains Long-Timescale Electrical Response in Lead Iodide Perovskite Thick Pellets

The favorable optoelectronic properties of metal halide perovskites have been used for X- and γ-ray detection, solar energy, and optoelectronics. Large electronic mobility, reduced recombination losses of the electron–hole pairs, and high sensitivity upon ionizing irradiation have fostered great attention on technological realizations. Nevertheless, the recognized mixed ionic-electronic transport properties of hybrid perovskites possess severe limitations as far as long-timescale instabilities and degradation issues are faced. Several effects are attributed to the presence of mobile ions such as shielding of the internal electrical field upon biasing and chemical interaction between intrinsic moving defects and electrode materials. Ion-originated modulations of electronic properties constitute an essential peace of knowledge to further progress into the halide perovskite device physics and operating modes. Here, ionic current and electronic impedance of lead methylammonium iodide perovskite thick pellets are independently monitored, showing self-consistent patterns. Our findings point to a coupling of ionic and electronic properties as a dynamic doping effect caused by moving ions that act as mobile dopants. The electronic doping profile changes within the bulk as a function of the actual ion inner distribution, then producing a specific time dependence in the electronic conductivity that reproduces time patterns of the type ∝t, a clear fingerprint of diffusive transport. Values for the iodine-related defect diffusivity in the range of Dion ∼ 10–8 cm2 s–1, which corresponds to ionic mobilities of about μion ∼ 10–6 cm2 V–1 s–1, are encountered. Technological realizations based on thick perovskite layers would benefit from this fundamental information, as far as long-timescale current stabilization is concerned.