Two-Dimensional Dion-Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations

Xiaotong Li; Weijun Ke; Boubacar Traoré; Peijun Guo; Ido Hadar; Mikaël Kepenekian; Jacky Even; Claudine Katan; Constantinos C Stoumpos; Richard D Schaller; Mercouri G Kanatzidis

doi:10.1021/jacs.9b06398

Two-Dimensional Dion-Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations

J Am Chem Soc. 2019 Aug 14;141(32):12880-12890. doi: 10.1021/jacs.9b06398. Epub 2019 Jul 31.

Authors

Affiliations

¹ Department of Chemistry , Northwestern University , 2145 Sheridan Road , Evanston , Illinois 60208 , United States.
² Univ Rennes, INSA Rennes, CNRS , Institut FOTON , UMR 6082 , Rennes F-35000 , France.
³ Center for Nanoscale Materials , Argonne National Laboratory , 9700 South Cass Avenue , Lemont , Illinois 60439 , United States.
⁴ Univ Rennes, ENSCR, INSA Rennes, CNRS , ISCR (Institut des Sciences Chimiques de Rennes) , UMR 6226 , Rennes F-35000 , France.
⁵ Department of Materials Science and Technology, Voutes Campus , University of Crete , Heraklion GR-70013 , Greece.

PMID: 31313919
DOI: 10.1021/jacs.9b06398

Abstract

Two-dimensional (2D) halide perovskites have extraordinary optoelectronic properties and structural tunability. Among them, the Dion-Jacobson phases with the inorganic layers stacking exactly on top of each other are less explored. Herein, we present the new series of 2D Dion-Jacobson halide perovskites, which adopt the general formula of A'A_n-1Pb_nI_3n+1 (A' = 4-(aminomethyl)pyridinium (4AMPY), A = methylammonium (MA), n = 1-4). By modifying the position of the CH₂NH₃⁺ group from 4AMPY to 3AMPY (3AMPY = 3-(aminomethyl)pyridinium), the stacking of the inorganic layers changes from exactly eclipsed to slightly offset. The perovskite octahedra tilts are also different between the two series, with the 3AMPY series exhibiting smaller bandgaps than the 4AMPY series. Compared to the aliphatic cation of the same size (AMP = (aminomethyl)piperidinium), the aromatic spacers increase the rigidity of the cation, reduce the interlayer spacing, and decrease the dielectric mismatch between inorganic layer and the organic spacer, showing the indirect but powerful influence of the organic cations on the structure and consequently on the optical properties of the perovskite materials. All A'A_n-1Pb_nI_3n+1 compounds exhibit strong photoluminescence (PL) at room temperature. Preliminary solar cell devices based on the n = 4 perovskites as absorbers of both series exhibit promising performances, with a champion power conversion efficiency (PCE) of 9.20% for (3AMPY)(MA)₃Pb₄I₁₃-based devices, which is higher than the (4AMPY)(MA)₃Pb₄I₁₃ and the corresponding aliphatic analogue (3AMP)(MA)₃Pb₄I₁₃-based ones.