Tuning Ionic and Electronic Conductivities in the “Hollow” Perovskite {en}MAPbI₃

The recently developed family of 3D halide perovskites with general formula (A)1–x(en)x(M)1–0.7x(I)3–0.4x (A = MA, FA; M = Pb2+, Sn2+; en = ethylenediammonium), often referred to as “hollow” perovskites, exhibits exceptional air stability and crystallizes in the high symmetry α phase at room temperature. These properties are counterintuitive, considering that these structures include the large divalent en cation charge-compensated by vacancies of Pb cations and I anions. Moreover, the understanding of their transport behavior is incomplete. To provide new insights into the ionic and electronic transport properties of these “hollow” perovskites, we performed DC polarization experiments and ab initio calculations on the {en}MAPbI3 material. We observe large variations of ionic and electronic conductivities with en concentration, which can be explained by charge and site arguments in conjunction with trapping effects. The latter is reflected by the increase of the activation energies for iodide ion transport with higher en content that we observe from both experimental and computational results. The connection between these transport phenomena and the stability of “hollow” perovskite materials and devices is discussed.