Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb2Br7

Lingling Mao; Peijun Guo; Mikaël Kepenekian; Ioannis Spanopoulos; Yihui He; Claudine Katan; Jacky Even; Richard D. Schaller; Ram Seshadri; Constantinos C. Stoumpos; Mercouri G. Kanatzidis

doi:10.1021/jacs.0c01625

Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb₂Br₇

Lingling Mao, Peijun Guo, Mikaël Kepenekian, Ioannis Spanopoulos, Yihui He, Claudine Katan, Jacky Even, Richard D. Schaller, Ram Seshadri, Constantinos C. Stoumpos^*, Mercouri G. Kanatzidis

^*Corresponding author for this work

Chemistry

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

67 Scopus citations

Abstract

Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb₂Br₇ ((A' = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A' cations and perovskitizer A cations generates the new (3AMP)_a(4AMP)_1-a(FA)_b(MA)_1-bPb₂Br₇ perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A' and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr₃ and consistent with the local distortion environment of the [Pb₂Br₇] framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb₂Br₇ has the smallest band gap while (4AMP)(MA)Pb₂Br₇ has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.

Original language	English (US)
Pages (from-to)	8342-8351
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	142
Issue number	18
DOIs	https://doi.org/10.1021/jacs.0c01625
State	Published - May 6 2020

Funding

This work was supported by the Department of Energy Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois and the International Institute for Nanotechnology (IIN). This work was supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation\u2013Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN).

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.0c01625

Cite this

Mao, L., Guo, P., Kepenekian, M., Spanopoulos, I., He, Y., Katan, C., Even, J., Schaller, R. D., Seshadri, R., Stoumpos, C. C., & Kanatzidis, M. G. (2020). Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb₂Br₇. Journal of the American Chemical Society, 142(18), 8342-8351. https://doi.org/10.1021/jacs.0c01625

@article{3b24ba4be3eb4bc485b63fe6d840cf67,

title = "Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb2Br7",

abstract = "Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb2Br7 ((A' = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A' cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A' and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.",

author = "Lingling Mao and Peijun Guo and Mika{\"e}l Kepenekian and Ioannis Spanopoulos and Yihui He and Claudine Katan and Jacky Even and Schaller, {Richard D.} and Ram Seshadri and Stoumpos, {Constantinos C.} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: This work was supported by the Department of Energy Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois and the International Institute for Nanotechnology (IIN). Funding Information: This work was supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation–Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = may,

day = "6",

doi = "10.1021/jacs.0c01625",

language = "English (US)",

volume = "142",

pages = "8342--8351",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "18",

}

Mao, L, Guo, P, Kepenekian, M, Spanopoulos, I, He, Y, Katan, C, Even, J, Schaller, RD, Seshadri, R, Stoumpos, CC & Kanatzidis, MG 2020, 'Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb₂Br₇', Journal of the American Chemical Society, vol. 142, no. 18, pp. 8342-8351. https://doi.org/10.1021/jacs.0c01625

TY - JOUR

T1 - Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb2Br7

AU - Mao, Lingling

AU - Guo, Peijun

AU - Kepenekian, Mikaël

AU - Spanopoulos, Ioannis

AU - He, Yihui

AU - Katan, Claudine

AU - Even, Jacky

AU - Schaller, Richard D.

AU - Seshadri, Ram

AU - Stoumpos, Constantinos C.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: This work was supported by the Department of Energy Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois and the International Institute for Nanotechnology (IIN). Funding Information: This work was supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant SC0012541 (synthesis and structural characterization of materials, M.G.K.). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Raman measurements were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation–Earth Sciences (EAR-1634415). The Raman system acquisition was supported by the NSF MRI proposal (EAR-1531583). This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under the allocation 2019-A0070907682 made by GENCI. J.E. acknowledges Institut Universitaire de France for funding. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/5/6

Y1 - 2020/5/6

N2 - Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb2Br7 ((A' = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A' cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A' and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.

AB - Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb2Br7 ((A' = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A' cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A' and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.

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DO - 10.1021/jacs.0c01625

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ER -

Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb₂Br₇

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CCDC 1999670: Experimental Crystal Structure Determination

CCDC 1999672: Experimental Crystal Structure Determination

CCDC 1999676: Experimental Crystal Structure Determination

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Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb2Br7

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ASJC Scopus subject areas

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CCDC 1999670: Experimental Crystal Structure Determination

CCDC 1999672: Experimental Crystal Structure Determination

CCDC 1999676: Experimental Crystal Structure Determination

Cite this

Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb₂Br₇