Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages

Yongping Fu; Xinyi Jiang; Xiaotong Li; Boubacar Traore; Ioannis Spanopoulos; Claudine Katan; Jacky Even; Mercouri G. Kanatzidis; Elad Harel

doi:10.1021/jacs.9b13587

Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages

Yongping Fu, Xinyi Jiang, Xiaotong Li, Boubacar Traore, Ioannis Spanopoulos, Claudine Katan, Jacky Even, Mercouri G. Kanatzidis, Elad Harel^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

112 Scopus citations

Abstract

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(EA_xMA_1-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.

Original language	English (US)
Pages (from-to)	4008-4021
Number of pages	14
Journal	Journal of the American Chemical Society
Volume	142
Issue number	8
DOIs	https://doi.org/10.1021/jacs.9b13587
State	Published - Feb 26 2020

Funding

Funding for this research was provided by the Enabling Quantum Leap program; an NSF EAGER grant under award number DMR-1838507. The structural characterization work was supported by the Office of Naval Research, under Grant N00014-17-1-2231 (X.L and M.G.K.). The calculation work was granted access to the HPC resources of [TGCC/INES/IDRIS] under the allocations 2019 A0010907682 made by GENCI. J.E. acknowledges financial support from the Institut Universitaire de France. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.9b13587

Cite this

@article{8f022455e86e462c93f02c84f5c73db3,

title = "Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages",

abstract = "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.",

author = "Yongping Fu and Xinyi Jiang and Xiaotong Li and Boubacar Traore and Ioannis Spanopoulos and Claudine Katan and Jacky Even and Kanatzidis, {Mercouri G.} and Elad Harel",

note = "Funding Information: Funding for this research was provided by the Enabling Quantum Leap program; an NSF EAGER grant under award number DMR-1838507. The structural characterization work was supported by the Office of Naval Research, under Grant N00014-17-1-2231 (X.L and M.G.K.). The calculation work was granted access to the HPC resources of [TGCC/INES/IDRIS] under the allocations 2019 A0010907682 made by GENCI. J.E. acknowledges financial support from the Institut Universitaire de France. This work made use of the EPIC facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = feb,

day = "26",

doi = "10.1021/jacs.9b13587",

language = "English (US)",

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AU - Fu, Yongping

AU - Jiang, Xinyi

AU - Li, Xiaotong

AU - Traore, Boubacar

AU - Spanopoulos, Ioannis

AU - Katan, Claudine

AU - Even, Jacky

AU - Kanatzidis, Mercouri G.

AU - Harel, Elad

N1 - Funding Information: Funding for this research was provided by the Enabling Quantum Leap program; an NSF EAGER grant under award number DMR-1838507. The structural characterization work was supported by the Office of Naval Research, under Grant N00014-17-1-2231 (X.L and M.G.K.). The calculation work was granted access to the HPC resources of [TGCC/INES/IDRIS] under the allocations 2019 A0010907682 made by GENCI. J.E. acknowledges financial support from the Institut Universitaire de France. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/2/26

Y1 - 2020/2/26

N2 - 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.

AB - 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.

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Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages

Abstract

Funding

ASJC Scopus subject areas

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CCDC 1984857: Experimental Crystal Structure Determination

CCDC 1984858: Experimental Crystal Structure Determination

CCDC 1984859: Experimental Crystal Structure Determination

Cite this

Cation Engineering in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites with Mixed Large A-Site Cations in the Cages

Abstract

Funding

ASJC Scopus subject areas

Access to Document

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Fingerprint

Datasets

CCDC 1984857: Experimental Crystal Structure Determination

CCDC 1984858: Experimental Crystal Structure Determination

CCDC 1984859: Experimental Crystal Structure Determination

Cite this