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

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^*

^*Corresponding author for this work

Chemistry

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

297 Scopus citations

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.

Original language	English (US)
Pages (from-to)	12880-12890
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	141
Issue number	32
DOIs	https://doi.org/10.1021/jacs.9b06398
State	Published - Aug 14 2019

Funding

This work was supported by the Office of Naval Research, under grant N00014-17-1-2231 (synthesis, structural characterization of materials, M.G.K.). X.L. acknowledges help by Dr. Jianchun Wang for calculation of the charge distribution in the 3AMPY and 4AMPY cations. M.K. acknowledges support from Region Bretagne through Boost’ERC LaHPerOS project. J.E. acknowledges the financial support from the Institut Universitaire de France. This research used the Center for Nanoscale Materials and the Advanced Photon Source at Argonne National Laboratory, both supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of the SPID (confocal microscopy) and EPIC (scanning electron microscopy) facilities of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS1542205), the Materials Research Science and Engineering Centers (NSF DMR-1720139), the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/jacs.9b06398

Cite this

@article{431518614f544259b7eebbb4d18c1e56,

title = "Two-Dimensional Dion-Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations",

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′An-1PbnI3n+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′An-1PbnI3n+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.",

author = "Xiaotong Li and Weijun Ke and Boubacar Traor{\'e} and Peijun Guo and Ido Hadar and Mika{\"e}l Kepenekian and Jacky Even and Claudine Katan and Stoumpos, {Constantinos C.} and Schaller, {Richard D.} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: This work was supported by the Office of Naval Research, under grant N00014-17-1-2231 (synthesis, structural characterization of materials, M.G.K.). X.L. acknowledges help by Dr. Jianchun Wang for calculation of the charge distribution in the 3AMPY and 4AMPY cations. M.K. acknowledges support from Region Bretagne through Boost{\textquoteright}ERC LaHPerOS project. J.E. acknowledges the financial support from the Institut Universitaire de France. This research used the Center for Nanoscale Materials and the Advanced Photon Source at Argonne National Laboratory, both supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of the SPID (confocal microscopy) and EPIC (scanning electron microscopy) facilities of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS1542205), the Materials Research Science and Engineering Centers (NSF DMR-1720139), the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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doi = "10.1021/jacs.9b06398",

language = "English (US)",

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T1 - Two-Dimensional Dion-Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations

AU - Li, Xiaotong

AU - Ke, Weijun

AU - Traoré, Boubacar

AU - Guo, Peijun

AU - Hadar, Ido

AU - Kepenekian, Mikaël

AU - Even, Jacky

AU - Katan, Claudine

AU - Stoumpos, Constantinos C.

AU - Schaller, Richard D.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: This work was supported by the Office of Naval Research, under grant N00014-17-1-2231 (synthesis, structural characterization of materials, M.G.K.). X.L. acknowledges help by Dr. Jianchun Wang for calculation of the charge distribution in the 3AMPY and 4AMPY cations. M.K. acknowledges support from Region Bretagne through Boost’ERC LaHPerOS project. J.E. acknowledges the financial support from the Institut Universitaire de France. This research used the Center for Nanoscale Materials and the Advanced Photon Source at Argonne National Laboratory, both supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of the SPID (confocal microscopy) and EPIC (scanning electron microscopy) facilities of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS1542205), the Materials Research Science and Engineering Centers (NSF DMR-1720139), the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/8/14

Y1 - 2019/8/14

N2 - 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′An-1PbnI3n+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′An-1PbnI3n+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.

AB - 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′An-1PbnI3n+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′An-1PbnI3n+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.

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

Abstract

Funding

ASJC Scopus subject areas

UN SDGs

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CCDC 1942548: Experimental Crystal Structure Determination

CCDC 1942549: Experimental Crystal Structure Determination

CCDC 1942543: Experimental Crystal Structure Determination

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

Abstract

Funding

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1942548: Experimental Crystal Structure Determination

CCDC 1942549: Experimental Crystal Structure Determination

CCDC 1942543: Experimental Crystal Structure Determination

Cite this