Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

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

doi:10.1021/acs.chemmater.9b01511

Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

Xiaotong Li, Peijun Guo, Mikaël Kepenekian, Ido Hadar, Claudine Katan, Jacky Even, Constantinos C. Stoumpos, Richard D. Schaller, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

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

113 Scopus citations

Abstract

Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C₄N₂H₁₂PbX₄ (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3-aminopyrrolidinium (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). Density functional theory calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.

Original language	English (US)
Pages (from-to)	3582-3590
Number of pages	9
Journal	Chemistry of Materials
Volume	31
Issue number	9
DOIs	https://doi.org/10.1021/acs.chemmater.9b01511
State	Published - May 14 2019

Funding

This work was supported by the Office of Naval Research, under Grant N00014-17-1-2231 (synthesis, structural characterization of materials, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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 Office of Naval Research, under Grant N00014-17-1-2231 (synthesis, structural characterization of materials, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.9b01511

Cite this

@article{dd7a7ec9b4334abd80ec4f1a90afd753,

title = "Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission",

abstract = "Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C4N2H12PbX4 (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3-aminopyrrolidinium (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). Density functional theory calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.",

author = "Xiaotong Li and Peijun Guo and Mika{\"e}l Kepenekian and Ido Hadar and Claudine Katan and Jacky Even 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, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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 Office of Naval Research, under Grant N00014-17-1-2231 (synthesis, structural characterization of materials, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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} 2019 American Chemical Society.",

year = "2019",

month = may,

day = "14",

doi = "10.1021/acs.chemmater.9b01511",

language = "English (US)",

volume = "31",

pages = "3582--3590",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "9",

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TY - JOUR

T1 - Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

AU - Li, Xiaotong

AU - Guo, Peijun

AU - Kepenekian, Mikaël

AU - Hadar, Ido

AU - Katan, Claudine

AU - Even, Jacky

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, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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 Office of Naval Research, under Grant N00014-17-1-2231 (synthesis, structural characterization of materials, stability studies, 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. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from the Agence Nationale pour la Recherche (TRANSHYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0010907682 made by GENCI. 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 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: © 2019 American Chemical Society.

PY - 2019/5/14

Y1 - 2019/5/14

N2 - Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C4N2H12PbX4 (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3-aminopyrrolidinium (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). Density functional theory calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.

AB - Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C4N2H12PbX4 (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3-aminopyrrolidinium (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). Density functional theory calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.

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U2 - 10.1021/acs.chemmater.9b01511

DO - 10.1021/acs.chemmater.9b01511

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ER -

Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

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Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1904557: Experimental Crystal Structure Determination

CCDC 1904556: Experimental Crystal Structure Determination

CCDC 1904555: Experimental Crystal Structure Determination

Cite this