Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

Li, Xiaotong; Cuthriell, Shelby A.; Bergonzoni, Ashanti; Dong, Hao; Traore, Boubacar; Stoumpos, Constantinos C.; Guo, P.; Even, Jacky; Katan, Claudine; Schaller, Richard D.; Kanatzidis, Mercouri G.

doi:10.1021/acs.chemmater.1c03605

Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

Journal Article · 07 February 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c03605· OSTI ID:1902979

Li, Xiaotong; Cuthriell, Shelby A.; Bergonzoni, Ashanti; Dong, Hao; Traore, Boubacar; Stoumpos, Constantinos C.; Guo, P.; Even, Jacky; Katan, Claudine; Schaller, Richard D.; Kanatzidis, Mercouri G.

Two-dimensional (2D) halide perovskites have outstanding optoelectronic properties, and they feature a variety of organic cation spacers and cage A-site cations that can be incorporated into their structures. It has recently been reported that the Goldschmidt tolerance factor can be relaxed and expanded in iodide 2D perovskites. Bromide 2D perovskites, whose multilayer structures and optical properties are much less studied, provide a great platform for studying structure-property relationships for 2D perovskites with large Asite cations. Herein, we report the synthesis and structure of three new 2D bromide perovskites-(BA)(2)(MHy)(2)Pb3Br10 (BA, butylammonium; MHy, methylhydrazinium), (BA)(2)(EA)(2)Pb3Br10 (EA is ethylammonium), and (BA)(2)(DMA)Pb2Br7 (DMA is dimethylammonium). We compared them with other 2D perovskites with different A-site cations but with the same spacer and layer thickness. Single-crystal structures show that the Pb-Br bonds are elongated to accommodate the large A-site cations. Additionally, the octahedra in (BA)(2)(MHy)(2)Pb3Br10 and (BA)(2)(EA)(2)Pb3Br10 are highly distorted, and their different stacking patterns of the inner and outer layers lead to the formation of the n = 3 phases. Density functional theory calculations show that 2D perovskites with larger A-site cations (e.g., DMA, MHy, and EA) have smaller band dispersions and larger effective masses than those with Cs+ and MA. (BA)(2)(MHy)(2)Pb3Br10 also exhibits one of the largest Rashba splittings in the literature. Structures with large cage cations also exhibit high band gaps within the same n number and short photoluminescence (PL) lifetimes. Temperature- and power-dependent PL measurements reveal that the broad shoulder in the PL peak originates from the trap states.

Research Organization:: Argonne National Laboratory (ANL)

Sponsoring Organization:: USDOE Office of Science - Office of Basic Energy Sciences; Institut Universitaire de France; European Union - Horizon 2020 Research and Innovation Programme; Yale University; Northwestern University

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1902979

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 3 Vol. 34; ISSN 0897-4756

Country of Publication:: United States

Language:: English

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CCDC 2111602: Experimental Crystal Structure Determination Xiaotong, Li,; A., Cuthriell, Shelby; Ashanti, Bergonzoni, https://doi.org/10.5517/ccdc.csd.cc28w96p The current record is supplemented by this dataset	dataset	January 2022
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Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

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