Mixed ionic-electronic conduction in Ruddlesden-Popper and Dion-Jacobson layered hybrid perovskites with aromatic organic spacers

The understanding of mixed ionic-electronic conductivity in hybrid perovskites has enabled major advances in the development of optoelectronic devices based on this class of materials. While recent investigations revealed the potential of using dimensionality effects for various applications, the implication of this strategy on mixed conductivity is yet to be established. Here, we present a systematic analysis of mixed conduction in layered (2D) hybrid halide perovskite films based on 1,4-phenylenedimethylammonium (PDMA) and benzylammonium (BzA) organic spacers in (PDMA)PbI4 and (BzA)2PbI4 compositions, forming representative Dion-Jacobson (DJ) and Ruddleson-Popper (RP) phases, respectively. Electrochemical measurements of charge transport parallel to the layered structure reveal mixed ionic-electronic conduction with electronic transport mediated by electron holes in both DJ and RP phases. In comparison to the 3D perovskites, larger activation energies for both ionic and electronic conductivities are observed which result in lower absolute values. While the layered perovskites still allow for a relatively efficient exchange of iodine with the gas phase, the lower change of conductivity on the variation of the iodine partial pressure compared with 3D perovskites is consistent with the exchange affecting only a fraction of the film, with implications for the encapsulating efficacy of these materials. We complement the analysis with a demonstration of the superior thermal stability of DJ structures compared to their RP counterparts. This can guide future explorations of dimensionality and composition to control the transport and stabilization properties of 2D perovskite films. Mixed ionic-electronic conduction is revealed in Dion-Jacobson (DJ) and Ruddlesden-Popper phases based on aromatic spacer cations, with higher activation energies for ion migration and thermal stability for DJ systems, relevant to their application.