ja9b13587_si_001.cif (1.16 MB)
Cation Engineering in Two-Dimensional Ruddlesden–Popper Lead Iodide Perovskites with Mixed Large A‑Site Cations in the Cages
datasetposted on 2020-02-14, 21:47 authored by Yongping Fu, Xinyi Jiang, Xiaotong Li, Boubacar Traore, Ioannis Spanopoulos, Claudine Katan, Jacky Even, Mercouri G. Kanatzidis, Elad Harel
The Goldschmidt tolerance factor in halide perovskites limits the number of cations that can enter their cages without destabilizing their overall structure. Here, we have explored the limits of this geometric factor and found that the ethylammonium (EA) cations which lie outside the tolerance factor range can still enter the cages of the 2D halide perovskites by stretching them. The new perovskites allow us to study how these large cations occupying the perovskite cages affect the structural, optical, and electronic properties. We report a series of cation engineered 2D Ruddlesden–Popper lead iodide perovskites (BA)2(EAxMA1–x)2Pb3I10 (x = 0–1, BA is n-butylammonium, MA is methylammonium) by the incorporation of a large EA cation in the cage. An analysis of the single-crystal structures reveals that the incorporation of EA in the cage significantly stretches Pb–I bonds, expands the cage, and induces a larger octahedral distortion in the inorganic framework. Spectroscopic and theoretical studies show that such structural deformation leads to a blue-shifted bandgap, sub-bandgap trap states with wider energetic distribution, and stronger photoluminescence quenching. These results enrich the family of 2D perovskites and provide new insights for understanding the structure–property relationship in perovskite materials.
BAperovskite cagessingle-crystal structuresiodide perovskitesEA cationphotoluminescence quenchingoctahedral distortion2 D halide perovskitessub-bandgap trap states2 D perovskitesblue-shifted bandgapperovskite materialshalide perovskites limitsstudies showCation EngineeringMA2 Pb 3Goldschmidt tolerance factorIodide Perovskitestolerance factor range